Polymer composition and preparation method thereof

Abstract

A polymer formed from a first monomer of vinylene carbonate and at least one second monomer different from the first monomer and free of glycidyl groups, wherein the molar ratio of the first monomer to the second monomer is from 4: 1 to 99: 1. The polymer, preferably the copolymer, dissolves the metal salt, and the composition of the copolymer and the metal salt may have an ionic conductivity of greater than 0.01 mS / cm. The polymer is suitable for various components of solid state batteries.

Description

[0001] Priority Claim

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 63 / 425,247, filed on November 14, 2022, the entire content of which is incorporated herein by reference. Field of the Invention

[0003] The present technology relates to a novel polymer, particularly a copolymer of vinylene carbonate compounds, and fibers and membranes made therefrom. More specifically, the present invention relates to this novel polymer, more specifically a copolymer, and a method for preparing the novel copolymer, and the use of the novel copolymer in battery separators, anodes, and / or cathodes. Background of the Invention

[0005] Metal-ion batteries, particularly lithium-ion batteries, are ubiquitous in modern electronic products that require increased performance, while demanding charging capabilities and increasingly stringent size limitations. In the early 1990s, the commercialization of lithium in batteries revolutionized battery technology, significantly improving the capacity and energy density of disposable cells and making them widely used today. The key to these advancements lies in the chemical and physical properties of lithium. Chemically, lithium has a high positive electronegativity and readily donates its valence electrons to form a stable configuration, making it an excellent battery anode component. During the charging step of commercial lithium-ion batteries, the graphite anode is reduced and accepts Li + ions to compensate for its internal charge. The cathode is oxidized and releases lithium ions (Li + ). During discharge, the graphite anode is oxidized and must release lithium ions, which are then accepted by the anode while the cathode is reduced. This high reactivity, combined with its lowest molecular weight among all metal elements, makes lithium an ideal material for developing more powerful and lighter batteries. Today, more environmentally friendly rechargeable lithium-ion batteries have been developed, making them suitable for modern high-usage applications that require frequent charging, such as portable electronic devices, military applications, and electric vehicles.

[0006] Traditional lithium-ion batteries use a liquid electrolyte solution to regulate the flow of lithium ions (i.e., electric current) between two electrodes capable of storing ions, known as the anode (negative electrode) and the cathode (positive electrode). There is usually a microporous polymer layer, such as a polyethylene or polypropylene layer, between the anode and the cathode, which aims to provide electron separation and ion conduction between the anode and the cathode. During discharge, lithium ions pass through the liquid electrolyte, through the pores in the polymer layer (referred to as the separator), and migrate from the anode to the cathode. This ion flow drives electrons to flow through the external circuit simultaneously, thus powering the connected device. During the charging cycle, the process is reversed, and ions flow from the cathode to the anode. Most commonly, the cathode consists of an aluminum foil current collector coated with a lithium cobalt oxide active material (LiCoO2, commonly known as LCO).

[0007] Due to the safety hazards of early lithium metal anodes, the anode has been using graphite active material on a copper foil current collector. This material is very stable, but the lithium storage capacity has been reduced to one-tenth. This trade-off results in the battery being able to be charged / discharged repeatedly, but the energy density has decreased (but is acceptable). Unfortunately, if the battery structure is damaged by external forces (such as being pierced by a nail, etc.) or charged too quickly (resulting in lithium metal plating rather than lithium intercalation between graphite flakes), rapid thermal runaway or explosion or fire may occur. Specifically, the formation of lithium plating on the graphite anode is not desirable because the formation of metal lithium dendrites can penetrate the porous separator and cause an internal short circuit in the battery when reaching the cathode. In addition, any lithium plating on top of the graphite may cause electrolyte decomposition, which in turn leads to gas release, expansion, and shortened cycle life. This can pose serious safety hazards to lithium-ion batteries, especially portable batteries used in passenger aircraft or portable batteries used in the increasingly popular electric vehicles. Most lithium-ion battery research has been dedicated to improving these inherent safety hazards; specifically, the uneven plating characteristics of lithium metal and the flammability of the liquid electrolyte solution.

[0008] Although the graphite anode is safer than the early lithium metal anodes, even when fully lithiated (LiC6), its energy capacity drops severely, to 372 mAh / g, which is almost one-tenth of the 3600 mAh / g of the solid lithium metal anode. A promising research area is the development of solid anodes with alkali metal anodes, which can provide three times or more energy density while maintaining a comparable uniform plating ability to the graphite anode in terms of charging cycle performance.

[0009] Another area of lithium-ion battery research focuses on developing a separator that can facilitate ion transport without a liquid electrolyte solution. Traditional separators are microporous permeable membranes that separate electron diffusion from ion diffusion. Composed of porous polyethylene or polypropylene (PE / PP), ion transport requires a liquid electrolyte solution. Many liquid lithium-ion batteries utilize lithium hexafluorophosphate salt dissolved in an organic carbonate solvent (e.g., ethylene carbonate and dimethyl carbonate) to facilitate ion movement between the anode and cathode. The liquid electrolyte solution has high conductivity at room temperature (e.g., a volume conductivity of 10 mS / cm). However, the traditional porous separator design reduces the conductivity to one percent due to the tortuosity of its pores. The separator plays a crucial role in battery safety. Polyolefin separators have low melting points (135 °C for PE and 165 °C for PP), resulting in poor thermal stability and potentially causing separator failure. When the temperature exceeds the melting point, the separator rapidly deteriorates, and thermal shrinkage can cause the cathode and anode to come into contact. This can lead to a thermal runaway reaction, resulting in overpressure, casing rupture, and ignition of the liquid electrolyte. By developing a thermally stable solid separator that can conduct ions without a flammable organic liquid electrolyte solution, these safety hazards can be significantly reduced.

[0010] Recently, efforts have been made to fabricate batteries with solid polymer electrolytes to reduce or eliminate the need for liquid electrolytes. The conventional polymer electrolyte used for this purpose is poly(ethylene oxide) (PEO), but the room-temperature ionic conductivity of PEO is several orders of magnitude lower than that of conventional organic liquid electrolyte solutions. Others have studied mixtures of PEO and PEO-based polymers with other components to fabricate solid electrolytes / membranes. For example, U.S. Patent No. 9,548,514 describes the use of poly(ethylene glycol) diacrylate (PEGDA) polymer, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a lithium salt, and succinonitrile (SCN) as a plasticizer, but these polymers tend to have low molecular weights and are waxy, lacking sustainable mechanical integrity. U.S. Patent No. 9,287,540 describes the use of heat-resistant particles (e.g., ceramics and other metal oxides) with traditional porous polymers (e.g., crosslinked thermosetting polymer particles and engineering thermoplastics). U.S. Patent No. 8,574,772 describes the use of garnet-type compounds and lithium ion conductors containing phosphate groups to form solid electrolytes. Although these types of solid polymers are alleged to minimize some of the safety issues associated with liquid electrolytes, they have reduced mechanical properties, including reduced flexibility and high reactivity with environmental air and moisture.

[0011] In view of the above, there is a need for novel, flexible, lightweight, and ion-conductive polymers for solid-state batteries with improved performance and to address the safety issues associated with traditional liquid lithium-ion electrolyte precursors. Summary of the Invention

[0013] The present technology relates to polymers and fibers and / or membranes made from these polymers. More specifically, the polymer is a copolymer comprising vinyl carbonate or a vinylidene derivative or analog copolymerized with certain compatible monomers, which can be designed for a wide range of uses such as fibers and / or membranes. These polymers can have a variety of applications and are particularly suitable for incorporation into various features of a battery after combination with a conductive metal salt. For example, the polymer can be made into a membrane, preferably the membrane is a conductive separator, or used as a solid electrolyte and as part of a battery anode and / or cathode. The separator made from the polymer of the present invention can be used as part of a battery. In some aspects, the polymer can be used as a solid electrolyte or an adhesive. The separator made from the polymer of the present invention can be used in a battery, particularly a metal ion battery, but not limited to lithium ion, sodium ion, potassium ion, magnesium ion, zinc ion, aluminum ion or calcium ion batteries. In one aspect, the polymer of the present invention forms a conductive membrane and is used as a single layer or a multi-layer separator. The present invention also relates to a method for synthesizing a polymer having physical and chemical properties useful for a separator, and a battery using the separator.

[0014] Ideally, the polymer of the present invention can dissolve a metal ion salt without using a liquid solvent and can form a conductive membrane and / or separator for a battery to separate the anode from the cathode. Additionally or alternatively, the polymer can be used as part of the cathode and anode, acting as a solid polymer electrolyte (when mixed with a conductive salt), and / or used as an adhesive to maintain the integrity of the electrode.

[0015] The battery of the present invention can be used to power various electronic applications, such as mobile phones, smart watches, tablets, laptops, cars, bicycles, drones, residences, and airplanes. Other uses include military applications, such as a backpack equipped with a battery, or any other portable application that requires power, such as drones, submarines, submersibles, tanks, and robots. Of course, the polymer is not limited to battery applications and can also be used in any application where polymer properties are beneficial, such as applications that require a high melting point. Non-limiting examples of applications of the polymer and its membrane include medical devices, aerospace, spacecraft, bearings, pumps, pistons, chromatography columns, and cables.

[0016] In one embodiment, the present disclosure relates to a copolymer comprising a vinyl carbonate compound as a first monomer as a copolymerization unit; and at least one additional monomer different from the first monomer and copolymerizable with the first monomer, provided that the at least one additional monomer does not contain a glycidyl group. In some aspects, the present disclosure relates to the copolymer described herein, provided that the at least one additional monomer does not contain an epoxy group and is not formed from a compound containing an epoxy group. The molar ratio of the first monomer to the at least one additional monomer is from 4:1 to 99:1.

[0017] In another embodiment, the present disclosure relates to a method for preparing the above copolymer, comprising: dissolving a vinylene carbonate compound in a solvent; contacting at least one additional monomer with the vinylene carbonate compound and a polymerization initiator in the solvent under reaction conditions sufficient to copolymerize the vinylene carbonate compound with the at least one additional monomer, thereby obtaining the copolymer in a reaction mixture; precipitating the copolymer from the reaction mixture under conditions effective to precipitate the polymer; and separating the copolymer from the reaction mixture. The solvent is optionally dimethyl sulfoxide, tetrahydrofuran or N-methyl-2-pyrrolidone. The polymerization initiator is optionally 2,2'-azobis(2,4-dimethylvaleronitrile). The reaction conditions sufficient to copolymerize the vinylene carbonate compound with at least one additional monomer optionally include a temperature of 40°C to 100°C. Advantageously, the method preferably has a copolymer yield greater than 50%, greater than 75% or greater than 90%.

[0018] In various embodiments, the first monomer is optionally selected from vinylene carbonate, derivatives of vinylene carbonate, and analogs of vinylene carbonate. The at least one additional monomer is optionally selected from or more optionally selected from: poly(ethylene glycol) methacrylate (PEGMA), 1,3-propane sultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylene ethylene carbonate (VEC), dimethyl vinylphosphonate (DMVP), maleic anhydride (MA), diethyl vinylphosphonate (DEVP), diethyl allylphosphonate (DEAP), or N-vinylpyrrolidone (NVP) (1-vinylpyrrolidin-2-one), N-methylmaleimide, vinylene sulfate, vinylene sulfite, ethylene vinylene sulfite, butadiene sulfone, vinylsulfonic acid (VSA), N,N-dimethylvinylsulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphospholane 2-oxide, metal salts of vinylsulfonic acid, metal salts of vinylphosphonic acid, metal salts of fluoro(vinyl)phosphinic acid, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metal salts of trifluoro(vinyl)boronic acid, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metal salts of 2-fluoro-2-vinyl-1,3,2-dioxaborolate-4,5-dione. In some alternative aspects, the at least one additional monomer comprises one or more of poly(ethylene glycol) methacrylate (PEGMA), vinylene ethylene carbonate (VEC), and / or dimethyl vinylphosphonate (DMVP). In some alternative aspects, the at least one additional monomer comprises one or more of 2,2,3,3,3-pentafluoropropyl methacrylate (PFMA), 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, and / or 2,2,3,3-tetrafluoropropyl methacrylate. The at least one additional monomer may comprise one, two, or more than two different additional monomers and is optionally selected from any of the above compounds.

[0019] In various aspects, the copolymer may be crosslinked or may not be crosslinked. The molecular weight of the copolymer is optionally greater than 50,000 Da, such as greater than 80,000 Da, greater than 100,000 Da, greater than 150,000 Da, greater than 200,000 Da, or greater than 250,000 Da. In terms of the molecular weight range, a preferred molecular weight range is from 250,000 Da to 2,000,000 Da, such as from 680,000 Da to 2,000,000 Da, and the density is 0.5 g / cm 3 to 2.5 g / cm 3Unless otherwise specified, the "molecular weight" used herein refers to the weight-average molecular weight (Mw). The melting point of the copolymer can be 200 °C or higher, or it may not exhibit a melting point, in which case its oxidation point is preferably 350 °C or higher.

[0020] In another embodiment, the present invention relates to a composition comprising the above copolymer and a metal salt. The metal salt optionally contains metal ions selected from alkali metals, alkaline earth metals, aluminum, and zinc. The metal salt is preferably a lithium salt. For example, the lithium salt can be selected from lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi. The ionic conductivity of the composition at 25 °C is preferably equal to or greater than 0.01 mS / cm (measured by electrochemical impedance spectroscopy). The decomposition onset current of the composition (relative to Li0 / Li+) is optionally equal to or greater than 4.5 V. The lithium salt content of the composition is optionally 20 wt% to 80 wt% (based on the total weight of the composition). In another embodiment, the present disclosure relates to a membrane, filament, nonwoven web, or woven fabric comprising the above composition.

[0021] In another embodiment, a solid-state battery is disclosed, comprising: a solid-state anode; a solid-state cathode; and a solid-state metal-ion conductive separator sandwiched between the solid-state anode and the solid-state cathode; wherein at least one of the solid-state anode and the solid-state metal-ion conductive separator comprises a component having the above composition. In a related aspect, the present disclosure relates to a solid-state lithium-ion battery, comprising: a solid-state anode capable of intercalating and deintercalating lithium ions; a solid-state cathode capable of intercalating and deintercalating lithium ions; and a solid-state lithium-ion conductive separator sandwiched between the anode and the cathode; wherein at least one of the solid-state anode, the solid-state cathode, and the solid-state separator comprises a component having the above composition. The solid-state lithium-ion conductive separator optionally comprises the above composition, wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi. The solid-state lithium-ion conductive separator optionally further comprises at least one of the following: (i) a polymer different from the copolymer; and (ii) an additive selected from clay, metal oxide, metal nitride, and lithium-conductive ceramic. In some aspects, the solid-state lithium-ion conductive separator comprises a lithium-conductive ceramic, wherein the lithium-conductive ceramic is selected from lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphorous sulfurchloride (LSPSCl), lithium germanium phosphorous sulfide (LGPS), lithium-conductive halide, closo-borate, and nido-borate. Optionally, the solid-state lithium-ion conductive separator is in the form of a film having a thickness of less than 30 microns, and the ionic conductivity of the film is 0.05 mS / cm or higher. The solid-state anode optionally comprises the above composition, wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0022] On the other hand, the present disclosure relates to a film comprising a polymer, the polymer comprising a first monomer of vinylene carbonate and a second monomer different from the first monomer and not having a glycidyl group; wherein the molar ratio of the first monomer to the at least one additional monomer is from 4:1 to 99:1. The film optionally further comprises a metal salt, has a thickness of less than 30 microns, and an ionic conductivity of 0.05 mS / cm or higher. The conductive film can be in the form of a separator or a conductive layer (in an electrode (e.g., a battery)). Brief Description of the Drawings

[0024] The nature and advantages of the disclosed technology can be further understood by referring to the remainder of the specification and the drawings.

[0025] Figure 1 Illustrates a polymer synthesis operation according to an embodiment of the present disclosure.

[0026] Figure 2 Illustrates a cross-sectional perspective view of a lithium metal-based battery according to an embodiment of the present disclosure.

[0027] Figure 3 Illustrates a cross-sectional perspective view of a solid separator for a solid-state lithium metal-based battery according to an embodiment of the present disclosure.

[0028] Figure 4(a) illustrates a steric polymerization reaction, and Figure 4(b) illustrates a copolymerization reaction according to an embodiment of the present disclosure.

[0029] Several of the figures are presented in schematic form. It should be understood that these figures are for illustrative purposes only and should not be considered to be drawn to scale unless explicitly stated. Additionally, as schematic diagrams, these figures are intended to aid understanding and may not include all aspects or information compared to the actual presentation and may contain exaggerations for illustrative purposes. In the drawings, similar components and / or features may have the same reference numerals. Additionally, various components of the same type may be distinguished by adding letters after the reference numeral to differentiate between similar components. If only the first reference numeral is used in the specification, the description applies to any similar component with the same first reference numeral, regardless of the letter. Detailed Description of the Invention

[0031] Introduction

[0032] Embodiments of the present invention relate to polymers and fibers and / or membranes made from these polymers. These fibers and / or membranes can be used as separators, or as part of the anode and / or part of the cathode. Notably, the polymer can be incorporated into part of the separator, or part of the anode (as an electrolyte), or part of the cathode (as an electrolyte). The separator can be used in batteries, particularly metal ion batteries, such as but not limited to lithium ion, sodium ion, potassium ion, magnesium ion, zinc ion, aluminum ion, or calcium ion batteries. The present disclosure also relates to methods for synthesizing the above polymers, which ideally have physical and chemical properties that are advantageous for use in separators and battery electrodes. Although mainly discussed in the context of energy storage systems, it should be understood that the polymers, fibers, and membranes described herein can also be used in other applications.

[0033] In one embodiment, the present disclosure relates to a polymer formed of at least a first monomer and a second monomer, the first monomer comprising a substituted or unsubstituted vinylene carbonate or an analogue or derivative thereof; the second monomer being different from the first monomer and not having a glycidyl group, and wherein the molar ratio of the first monomer to the second monomer is from 4:1 to 99:1. In one embodiment, the present disclosure relates to a copolymer comprising the following monomers as copolymer units: a vinylene carbonate compound as the first monomer; and at least one additional compound (e.g., and an additional or second monomer) different from the first monomer and copolymerizable with the first monomer; provided that the at least one additional compound does not contain a glycidyl group; wherein the molar ratio of the first monomer to the at least one second monomer is from 4:1 to 99:1. In some aspects, the at least one additional monomer does not contain an epoxy group and is not formed from a compound containing an epoxy group. In another embodiment, the present disclosure relates to a method for synthesizing the copolymer, the method comprising: dissolving a vinylene carbonate compound in a solvent; contacting at least one additional compound with the vinylene carbonate compound and a polymerization initiator in the solvent under reaction conditions sufficient to copolymerize the vinylene carbonate compound (first monomer) and the at least one additional compound (second monomer) to obtain a copolymer in the reaction mixture; precipitating the copolymer from the reaction mixture under conditions effective to precipitate the polymer; and separating the copolymer from the reaction mixture.

[0034] In another embodiment, the present disclosure relates to a method for synthesizing the polymer, the method comprising: (i) providing a first monomer having a substituted or unsubstituted vinylidene in a solvent; (ii) metering in a second monomer, preferably in the same solvent, wherein the second monomer is different from the first monomer and does not contain a glycidyl group; (iii) contacting the first monomer with the second monomer in the presence of the solvent and an initiator under reaction conditions sufficient to form a reaction mixture comprising the polymer; and (iv) mixing a precipitant (e.g., water or methanol) with the reaction mixture under conditions effective to precipitate the polymer.

[0035] In these aspects, the molar ratio of the first monomer to the second monomer for forming the polymer is preferably from 4:1 to 99:1.

[0036] Polymers and Their Preparation Methods

[0037] See Figure 1, showing selected operations of a method 10 for synthesizing a polymer. In operation 15, a first monomer can be provided, preferably in a reaction solvent. In operation 20, a second monomer can be provided, more preferably metered into the first monomer. Alternatively, the second monomer can be provided before the first monomer. In some embodiments, a third monomer (or optionally more than three monomers) can be provided (optionally metered in) in operation 25. Of course, any addition order can be employed depending on the specific monomers selected. Thus, for example, the optional third monomer can be added before, after, or between the provision or metering of the first and second monomers. In operation 30, the monomers comprising the first monomer, the second monomer, and the third monomer (if present) can be contacted with each other under reaction conditions sufficient to react and form a reaction mixture comprising a polymer, preferably in the presence of a solvent and an initiator. In operation 35, method 10 can include recovering the polymer precipitate product, optionally by adding a precipitant under conditions effective to precipitate the polymer product, after contacting the monomers and after a period of time required to synthesize the polymer product.

[0038] In the present disclosure, the first monomer is unsubstituted or substituted vinylene carbonate or an analogue or derivative thereof. As used herein, "analogue" refers to a compound having a structure similar to another compound (e.g., vinylene carbonate), but differing therefrom in one component. Importantly, the analogue contains a ring with a carbonate bond and an internal double bond. The term "derivative" refers to a chemical compound formed from a parent compound (e.g., vinylene carbonate) through one or more chemical reactions, having a structure similar to the parent compound, but differing in one or more components, functional groups, atoms, etc.

[0039] Thus, the first monomer can be unsubstituted vinylene carbonate, as shown in the following formula (I):

[0040]

[0041] On the other hand, the first monomer can be a substituted vinylene carbonate or an analogue or derivative of vinylene carbonate. For example, the substituted vinylene carbonate can have the following formula (II), where R1 and R2 are independently selected from any moieties that are the same or different from each other, provided that at least one of R1 and R2 is not hydrogen. In some non-limiting embodiments, the substituents on the vinylene carbonate can be selected from any substituted or unsubstituted alkyl, alkenyl, alkynyl, sultone, sulfone, maleate, phosphonate, cyclobutenesulfone, or maleimide group. In some alternative embodiments, in addition to the substituted or unsubstituted vinylene group, the first monomer can also contain an ether group or a carbonyl group, such as an aldehyde, carboxylic acid, amide, or ester.

[0042]

[0043] Exemplary substituted vinylene carbonate

[0044] Of course, even if other substituted vinylene carbonate compounds, analogs, and derivatives are not covered by formula (II), they are possible and also fall within the scope of the present disclosure.

[0045] Homopolymers of vinylene carbonate are generally obtained in low molecular weight and formed in low yields. Such homopolymers also exhibit low ionic conductivity in the presence of metal salts, which can be explained by the low mobility of the poly(vinyl carbonate) (PVCA) chains. The building block of PVCA is a five-membered carbonate ring, which cannot rotate freely around its connecting bond due to steric hindrance. Therefore, the PVCA homopolymer chains cannot coordinate well with small cations (such as Li + ions), as shown in Fig. 4(a) (the carbonate moiety is omitted for simplicity). In addition, vinylene carbonate homopolymers have low solubility in solvents and are denatured by interaction with polar solvents. Due to the strong rotational hindrance of the homopolymer, such strong solvents will break the polymer chains into fragments during the solvation process. Therefore, vinylene carbonate homopolymers are difficult to dissolve in organic solvents and usually need to be processed into fine particles before dissolution, and heating and long-term mixing are required to form a homogeneous solution. In addition, vinylene carbonate homopolymer solutions are unstable, which limits the ability for further processing. Therefore, in battery applications, vinylene carbonate is usually polymerized in situ, and it is impossible to remove impurities and perform further modification.

[0046] Without being bound by theory, it has now been found that during the polymerization process, incorporating a second monomer (also referred to herein as an additional compound or additional monomer) that can copolymerize with the first monomer into the vinylene carbonate polymer chain can improve the rotation and mobility of the polymer by reducing the overall steric hindrance, which surprisingly and unexpectedly improves the coordination of metal cations (such as but not limited to lithium cations) and increases the conductivity of the polymer at low temperatures. In this way, the second monomer can act as a "spacer" monomer in the copolymer. Fig. 4(b) shows some of the potential interactions allowed by this increased polymer flexibility.

[0047] The second monomer or at least one additional compound copolymerizable with the first monomer may include any monomer different from the first monomer, provided that the second monomer does not contain a glycidyl group, which may have an adverse effect on the total yield and properties of the copolymer. Advantageously, the polymer, particularly the copolymer described herein, has improved stability in an organic solvent (e.g., DMSO), such that the polymer is not easily decomposed in the organic solvent, while also preferably providing a polymer weight average molecular weight greater than 50,000 Da, such as greater than 80,000 Da, greater than 100,000 Da, greater than 150,000 Da, greater than 200,000 Da, greater than 250,000 Da, greater than 500,000 Da, or greater than 680,000 Da. It has been found that using one or more additional compounds as comonomers in combination with the first monomer can achieve polymerization reactions that would otherwise not be possible, with a yield greater than 50%, such as greater than 60%, greater than 70%, greater than 75%, greater than 80%, greater than 90%, or even approaching 100%, and can form copolymers with a higher molecular weight (Mw) than similar reactions. It has also been found that using such one or more second monomers in combination with the first monomer can form copolymers with desirable mechanical and electrochemical properties, which are suitable for various battery components as described above.

[0048] In one embodiment, the at least one additional compound (second monomer) copolymerizable with the vinylene carbonate compound does not include linear α-olefins, such as ethylene and propylene. Additionally, the second monomer copolymerizable with the first monomer preferably does not include ethylene carbonate or propylene carbonate. Further, the second monomer preferably does not include diol acrylates, such as butanediol and hexanediol, or ethylene glycol acrylates, such as triacrylate, diacrylate, and monoacrylate. However, any form of the linear α-olefin or the excluded monomers described above can be used as a third monomer.

[0049] In one embodiment, the disclosed polymer made from vinylene carbonate or its analogs or derivatives (collectively referred to as "vinylene carbonate compounds") and the second monomer does not require the use of ethylene oxide (one or more) or nitrile compounds, such as succinonitrile (SCN). Thus, the copolymer is preferably a non-crosslinked copolymer.

[0050] In an embodiment, the additional compound (second monomer) copolymerizable with the first monomer contains a substituted or unsubstituted vinylidene group, which can be characterized by the formula -CH=CH-. That is, the second monomer can be any additional compound containing a vinylidene group, i.e., R 3 -CH=CH-R 4 where R 3 and R 4Selected from any moieties, the same as or different from each other. The second monomer may or may not contain at least one ring structure, which may be a ring structure of 3, 4, 5, or 6 atoms. In this regard, R 3 and R 4 moieties may be interconnected with each other through one or more intermediate atoms to form a ring structure. In some aspects, the intermediate atoms may include an alkyl chain, an alkenyl chain, or a carbonate group (such as vinylene carbonate). In some aspects, a substituted or unsubstituted vinylidene includes a substituted or unsubstituted vinyl.

[0051] In other embodiments, the second monomer may contain a substituted vinylidene of the formula -CR 5 =CR 6 -, where R 5 and R 6 are independently selected from any moieties that are the same as or different from each other, provided that at least one of R 5 and R 6 is not hydrogen. That is, the second monomer may contain any compound containing a substituted vinylidene, i.e., R 3 -CR 5 =CR 6 -R 4 , where R 3 、R 4 、R 5 and R 6 are independently selected from any moieties that are the same as or different from each other, provided that at least one of R 5 and R 6 is not hydrogen. It should be noted that in some aspects, R 3 、R 4 、R 5 and R 6Two or more of the moieties may be interconnected via one or more intervening atoms to form a cyclic structure. In various alternative embodiments, the second monomer may be an unsaturated cyclic carbonate. In some specific exemplary embodiments, the second monomer (or at least one additional compound copolymerizable with the first monomer) may be 1,3 - propanesultone (PES), bis(2,2,2 - trifluoroethyl) maleate (TFM), vinylene carbonate (VEC), dimethyl vinylphosphonate (DMVP), maleic anhydride (MA), diethyl vinylphosphonate (DEVP), diethyl allylphosphonate (DEAP), or N - vinylpyrrolidone (NVP) (1 - vinylpyrrolidin - 2 - one), N - methylmaleimide, vinylene sulfate, vinylene sulfite, ethylene vinyl sulfite, butadiene sulfone, vinylsulfonic acid (VSA), N,N - dimethylvinylsulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2 - vinyl - 1,3,2 - dioxaphospholane - 2 - oxide, metal salts of vinylsulfonic acid, metal salts of vinylphosphonic acid, metal salts of fluoro(vinyl)phosphinic acid, 1 - vinylpyrrolidine - 2,5 - dione, vinylboronic acid, metal salts of trifluoro(vinyl)boronic acid, 2 - vinyl - 1,3,2 - dioxaborolane - 4,5 - dione, and metal salts of 2 - fluoro - 2 - vinyl - 1,3,2 - dioxaborolane - 4,5 - dione. For monomers containing a metal cation, the cation may be selected from any metal, but is preferably selected from lithium, sodium, potassium, calcium, and magnesium. In some preferred embodiments, the second monomer is poly(ethylene glycol) methacrylate (PEGMA), vinylene carbonate (VEC), or dimethyl vinylphosphonate (DMVP). Other compounds suitable for use as the second monomer include any one of butyl cyanoacrylate, n - butyl acrylate, 2 - acetoacetoxyethyl methacrylate, and pentafluoropropyl methacrylate.

[0052] The relative amounts and ratios of the first monomer to the second monomer or at least one additional compound used to form the copolymer can vary. In a preferred embodiment, the molar ratio of the first monomer to the second monomer or at least one additional compound used to form the copolymer can be from 4:1 to 99:1, such as 8:1 to 99:1, 15:1 to 99:1, 25:1 to 99:1, or 75:1 to 99:1. In terms of the upper limit, the molar ratio of the first monomer to the second monomer or at least one additional compound can be less than 98:1, less than 97:1, less than 96:1, less than 95:1, less than 90:1, less than 85:1, less than 80:1, less than 75:1, or less. Conversely, in terms of the lower limit, the molar ratio of the first monomer to the second monomer or at least one additional compound can be greater than 4:1, greater than 5:1, greater than 6:1, greater than 7:1, greater than 8:1, greater than 9:1, greater than 10:1, greater than 15:1, greater than 20:1, greater than 25:1, greater than 30:1, or greater than 75:1 or higher. If the ratio of the first monomer to the second monomer or at least one additional compound is too low (too many spacer monomers), such as less than 4:1, the resulting polymer may be too soft. If the ratio of the first monomer to the second monomer is too high (too few spacer monomers), the resulting polymer may be too brittle. Without being bound by theory, it has now been found that using the above ratios results in a flexible, higher molecular weight polymer that has better solubility in solvents and higher ionic conductivity, relative to a polymer formed from only the first monomer.

[0053] The molar percentage of the first monomer in the polymer can be greater than 80%, and can be greater than 82%, greater than 84%, greater than 86%, greater than 88%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, or greater than 98%, or more, based on the total molar amount of all monomers used to form the monomer. In terms of the range, the molar percentage of the first monomer in the polymer can be from 80% to 99%, 85% to 99%, or 90% to 99%.

[0054] The molar percentage of the total amount of the second monomer or at least one additional compound in the copolymer can be less than 20 mol%, such as less than 15 mol%, less than 14 mol%, less than 13 mol%, less than 12 mol%, less than 11 mol%, less than 10 mol%, less than 9 mol%, less than 8 mol%, less than 7 mol%, less than 6 mol%, less than 5 mol%, less than 4 mol%, less than 3 mol%, less than 2 mol%, or less. In terms of the range, the content of the second monomer can be from 0.1 to 20 mol%, such as from 0.1 to 15 mol%, from 0.1 to 12 mol%, from 0.1 to 10 mol%, from 0.1 to 8 mol%, or from 0.1 to 6 mol%.

[0055] In one aspect, at least one additional compound copolymerizable with the first monomer may comprise two additional compounds, namely a second monomer and a third monomer, and the third compound or third monomer may be selected from any of the above-mentioned first monomer or second monomer, provided that it is different from the monomers selected for the first monomer and the second monomer. Thus, for example, the optional third monomer may be selected from PEGMA, VEC, and DMVP, provided that the third monomer is different from the second monomer used.

[0056] As previously described, in operation 30, the monomers (including the first monomer, the second monomer, and the optional third monomer, if present) may be contacted with each other in a reactor under conditions effective to react and form a copolymer. The specific vessel and reaction conditions employed may vary widely. In some aspects, the monomers are mixed together in a reactor, which may be any suitable polymerization reactor capable of withstanding the specific temperature and pressure conditions employed during the polymerization process. In one aspect, the reactor is a vial, a round-bottom flask, or a steel vessel, or a larger commercial polymerization reactor. The polymer may be synthesized using a continuous, semi-batch, or batch process. The monomers may be contacted at a temperature suitable for the polymerization process, which is typically determined by the initiator used. In some non-limiting embodiments, the temperature range may be from 40 to 100 °C, such as from 40 to 80 °C or from 50 to 70 °C. The reaction may be carried out at atmospheric or elevated pressure, such as from 1 to 5 atmospheres. The reaction may be carried out with a residence time of from several hours to several days, preferably from 0.5 to 21 days, more preferably from 0.5 to 14 days, even more preferably from 0.5 to 7 days or from 0.5 to 2 days. The order of addition of the monomers may also vary widely, which mainly depends on the reactivity of the selected monomers. Generally, all the monomers are not added at once. Instead, in one aspect, the monomer with the lowest reactivity is added first, and then the monomer with the highest reactivity is added or metered in. In one aspect, the first monomer is added to the reactor before the second monomer. In another aspect, the second monomer is added to the reactor before the first monomer. In another aspect, the first and second monomers are added to the reactor at least partially simultaneously. The monomers may also be added in stages (metered in) as needed.

[0057] In operation 30, the monomers may be contacted in the presence of a solvent and / or an initiator. In a preferred aspect, the solvent is selected based on its ability to dissolve the reagents (monomers and initiator) and the resulting polymer product. In addition, the solvent should be relatively inert and not react under the reaction conditions. The solvent should also be a liquid near the reaction temperature as well as at room temperature. The solvent may be or include, for example, any solvent suitable for dissolving the provided monomers, such as but not limited to dimethyl sulfoxide (DMSO), tetrahydrofuran, or N-methyl-2-pyrrolidone (NMP).

[0058] In a preferred aspect, the polymerization reaction is a free radical polymerization reaction. Thus, an initiator can be provided to react with one or more monomers to initiate the reaction and form one or more intermediate compounds capable of continuously linking with one or more other monomers. In an exemplary embodiment, the initiator can be or can include azobisisobutyronitrile (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile). Other commercially available initiators include bifunctional peroxides such as (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane) or diazo compounds such as VAZO TM 52. The amount of initiator used can vary widely, but in some exemplary embodiments, it can range from 0.01 to 1 mol%, such as 0.01 to 0.8 mol%, 0.02 to 0.5 mol%, or 0.1 to 0.4 mol%.

[0059] On the other hand, an organic solvent (such as an alkane like hexane) can be used as a "non-solvent" medium to improve the mixing of the monomers and the initiator without dissolving them. In this way, the reaction can be carried out without a true solvent and without the need for a "pure" reaction.

[0060] In operation 35, the specific steps for recovering the resulting precipitate or the synthesized polymeric material can vary widely. On the one hand, the steps for recovering the product include dropping the reaction solution containing the product into a non-solvent (such as methanol), which causes the product with a sufficiently high molecular weight to precipitate and retains the ultra-low molecular weight components in a solvated form. Other possible non-solvents that can be used to precipitate the polymer include water, alkanes (such as hexane), toluene, ethanol, isopropanol, propanol, etc. The solvent can be slowly metered in to form a filamentous precipitate of the polymer. Then the supernatant is decanted, the product is washed with additional non-solvent (such as MeOH), and then ground with the non-solvent (such as MeOH) for 1 to 48 hours, such as for a period of 20 to 28 hours. Then the non-solvent is decanted and the grinding can be optionally repeated. The separated product can be optionally dried under vacuum at a temperature of 20 to 60 °C, such as 30 to 50 °C, 35 to 45 °C, or about 40 °C, for a period of 0.5 to 4 days, such as 1 to 3 days or about 2 days, to obtain a grayish-white polymeric product filament. On the other hand, the polymer can be redissolved in a solvent and the process can be repeated.

[0061] The molecular weight of the polymer may vary mainly depending on its intended use. For some uses, for example, when used as an electrolyte in an electrode layer, it may be preferable to use a soft or waxy polymer with a relatively low molecular weight, while a polymer for a separator is preferably a harder and higher molecular weight polymer. Similarly, a "sticky" polymer with a medium molecular weight can be beneficially used as an adhesive composition, such as an adhesive composition in an electrode. The precipitation step, especially the non-solvent used in the precipitation step, is crucial for determining the molecular weight of the polymer product. For example, choosing hexane as the non-solvent precipitant can form a polymer with extremely high viscosity and high molecular weight, suitable for use as a separator. Such polymers may require crushing equipment (such as a rock crusher) to crush large rock-like polymer products and form polymer powders that can be used to prepare battery separator slurries. The molecular weight of the polymer generally corresponds to the viscosity of the polymer in a 5-10 weight percentage solution and can be qualitatively measured based on this viscosity. The preferred viscosity can vary depending on the desired application. For example, for blade casting separators or for spinning fibers, a polymer with a viscosity of 500 cP to 1000 cP (such as 500 to 750 cP or 750 to 1000 cP) may be required, but viscosities outside these ranges are also possible, depending on factors such as the second monomer used.

[0062] Polymer and Membrane Properties

[0063] The polymers of the present disclosure have unique structural and chemical properties that make them very useful in or as separators. Separators require the use of polymer membranes with certain thickness, pore size, pore size distribution, porosity, and chemical stability. In addition to these properties, separators also have functional properties such as electrical resistance (ER), permeability, and transference number.

[0064] Depending on the intended use of the polymer and the preparation method (e.g., precipitation method), the polymer can have a relatively low, medium, or high molecular weight. In some non-limiting embodiments, the weight-average molecular weight of the polymer can be greater than 50,000 Da, for example, greater than 80,000 Da, greater than 100,000 Da, greater than 150,000 Da, greater than 200,000 Da, greater than 250,000 Da, greater than 250,000 Da, greater than 500,000 Da, greater than 680,000 Da, greater than 750,000 Da, greater than 1,000,000 Da, greater than 1,500,000 Da, or greater than 2,000,000 Da. In some embodiments, the molecular weight of the polymer can be less than 2,000,000 Da, less than 1,500,000 Da, less than 1,000,000 Da, less than 750,000 Da, less than 500,000 Da, or less than 250,000 Da. In terms of the molecular weight range, the molecular weight can be from 750,000 to 2,500,000 Da, for example from 900,000 to 1,300,000 Da, or from 1,000,000 to 2,000,000 Da.

[0065] Similar to the molecular weight, the density of the polymer can also vary depending on its intended use. In some aspects, for example, the density of the polymer is greater than 0.5 g / cm 3 , for example greater than 0.6 g / cm 3 , greater than 0.7 g / cm 3 , greater than 1.0 g / cm 3 , or greater than 1.5 g / cm 3 , and less than 2.5 g / cm 3 . In terms of the range, the density of the polymer can be from 0.5 to 2.5 g / cm 3 , from 0.5 to 2.0 g / cm 3 , from 0.5 to 1.5 g / cm 3 , from 0.5 to 1.0 g / cm 3 , from 0.6 to 0.9 g / cm 3 , or from 0.7 to 0.8 g / cm 3 .

[0066] Depending on the selected monomers, the polymer may or may not have a melting point. In most cases, the polymer does not have a melting point, which means that as the temperature of the polymer increases, it will oxidize (burn) in air before reaching the melting point. Thus, in some embodiments, the polymer does not melt, and the oxidation point is higher than 350 °C, such as higher than 400 °C or higher than 450 °C, optionally 350 °C to 450 °C or 375 °C to 425 °C. Even so, considering the case of certain second monomers, the polymer may have a melting point. In this case, the melting point is preferably higher than 200 °C, higher than 300 °C or higher than 400 °C.

[0067] The dispersity of the polymers of the present disclosure is greater than about 1.5, greater than about 2.0, greater than about 2.5, greater than about 3.0, greater than about 3.2 or greater than about 3.5. In terms of ranges, the dispersity can be from about 1.5 to about 6, such as from about 2 to about 5, from about 2.5 to about 4, from about 3 to about 4, from about 3.2 to about 4 or from about 3.5 to about 4. The molecular weight of the polymers of the present disclosure is optionally greater than 50,000 Da, such as greater than 80,000 Da, greater than 100,000 Da, greater than 150,000 Da, greater than 200,000 Da or greater than 250,000 Da. In one embodiment of the polymers of the present disclosure, the dispersity of the polymer is greater than about 1.5 (e.g., greater than about 2.0, greater than about 2.5, greater than about 3.0, greater than about 3.2 or greater than about 3.5), and the molecular weight is greater than 50,000 Da, such as, greater than 80,000 Da.

[0068] For many applications, especially battery applications, an important feature is that the polymer should have a relatively high ionic conductivity, which is determined by electrochemical impedance spectroscopy (EIS). It is noted that the copolymer itself does not have ionic conductivity, but when a metal salt is added, it can advantageously exhibit high conductivity. Thus, in one aspect, the present disclosure provides a composition comprising the copolymer described in the foregoing aspects and a metal salt.

[0069] On the one hand, the metal salt comprises metal ions selected from alkali metals, alkaline earth metals, aluminum, and zinc. On the one hand, the metal salt is a lithium salt selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0070] Accordingly, the conductive film prepared according to the present invention is preferably made of a polymer that binds to a metal salt to form a polymer blend composition (specifically, a conductive polymer blend) or more specifically, a composition comprising the copolymer of the present disclosure as described above. Then, the polymer blend can be dissolved in a solvent and evaporated after doctor blading to form the conductive film as described herein. In various aspects, the conductive film or separator of the present invention can be made from a conductive polymer blend by any known film-making technique, such as doctor blading or casting, blow molding, extrusion, or spraying.

[0071] The polymers of the present disclosure can be made into films or separators in a variety of ways. Currently, two commercial methods are mainly used: dry process and wet process. In a typical dry process, the polymer is made by a blown film process, in which the polymer melt is extruded from an annular die and then collapsed or flattened using nip rolls. In this process, the tubular film is filled with air, and air is continuously blown into the tubular film to cool and solidify the film. A cast film process can also be used to produce films or separators from the polymers of the present invention. In the cast process, the extruded film is rolled on a cooling roll to rapidly quench the melt. Then, an annealing process can be performed on the film or separator to orient the crystalline film or separator structure. The film or separator can be further cold drawn or hot drawn.

[0072] The wet process can include multiple steps, including mixing, heating, extrusion, stretching, and removal of additives. The polymer in this process can be mixed with a solution and other additives (including metal salts in the case of making a separator) to form a homogeneous heated solution. The resulting solution can be extruded through a tablet die to form a gel-like film, which is then stretched or oriented. Subsequently, the additives and volatile solvents used can be removed by heating during the drying process. In some embodiments, the polymers of the present disclosure can be formed into non-woven materials or fabrics. The non-woven fabric or fabric can be prepared by continuously spinning filament fibers onto a moving belt. The fibers are made by extruding the polymer into a flowing polymer melt. After the spinning process, the polymer presents as fine continuous filaments. Then, the filaments can be cooled, stretched, solidified, and transformed into mats. These mats can then be used as separators or form part of an anode or cathode. These mats can alternatively be combined with ceramics to be used as separators. In a preferred embodiment, the polymers of the present disclosure are made into fibers using an electrospinning process.

[0073] The ionic conductivity described herein was measured using an electrochemical impedance spectroscopy analyzer on a conductive film formed from the polymer of the present disclosure and LiTFSI at a polymer:LiTFSI mass ratio of 1:1.5, where the polymer was cast into a film before analyzing the conductivity.

[0074] The conductive film of the present disclosure optionally has a room temperature ionic conductivity greater than 0.01 mS / cm measured in mS / cm by an electrochemical impedance spectrometer, for example, greater than 0.05 mS / cm, greater than 0.1 mS / cm, greater than 0.15 mS / cm, greater than 0.2 mS / cm, or greater than 0.3 mS / cm. In terms of range, the conductivity range of the conductive film can be from 0.01 to 0.3 mS / cm, for example, 0.05 to 0.3 mS / cm, 0.1 to 0.3 mS / cm, 0.15 to 0.3 mS / cm, or 0.2 to 0.3 mS / cm. These conductivities are very advantageous compared to conventional liquid electrolyte diaphragms, which comparably have relatively low conductivities at room temperature. Similarly, conventional PEO solid polymer electrolytes containing LiTSFI salt can have a conductivity as low as 0.001 mS / cm at room temperature.

[0075] In one embodiment, a film made of the polymer of the present disclosure, preferably when used as a diaphragm, has a thickness less than 25 μm, less than 20 μm, less than 15 μm, less than 12 μm, less than 10 μm, less than 7 μm. The thickness of the film of the present invention is generally in the range of 5 μm to 25 μm, for example, 5 μm to 15 μm, or 7 μm to 15 μm. The thickness of the diaphragm made of the polymer (more specifically, the copolymer composition) of the present disclosure can also be varied as needed to be used as part of a cathode layer or an anode layer. The thickness of the film or diaphragm is measured according to ASTM D5947-96.

[0076] In another embodiment, the thickness range of the conductive film of the present disclosure is from 1 to 300 μm, for example, 10 to 250 μm, 50 to 250 μm, 50 to 200 μm, or 70 to 200 μm. When the film is intended to be used as a battery diaphragm, a smaller thickness may be preferred, for example, 5 to 25 μm, for example, 5 to 20 μm, 5 to 15 μm, or 5 to 10 μm. In other aspects, the thickness of the conductive film can be greater than 10 μm, for example, greater than 50 μm, greater than 70 μm, greater than 100 μm, greater than 200 μm, or greater than 300 μm.

[0077] Porosity is a very important property for the high permeability of the film, especially for a film used as a porous diaphragm. Depending on the application, it may be preferred to have a more uniform porosity to ensure unobstructed flow of ionic current (i.e., lithium ions) between the cathode and the anode. The porosity of the film or diaphragm of the present invention is measured using ASTM D-2873. The porosity of the film or diaphragm of the present invention is optionally greater than 40%, greater than 45%, greater than 50%, greater than 55%, or greater than 60%. In another embodiment, the porosity of the film or diaphragm is in the range of 30% to 70%, for example, 40% to 65%, 45% to 65%, or 50% to 65%.

[0078] When manufacturing the membrane or separator of the present invention, the membrane or separator is optionally stretched longitudinally, transversely, or both. Especially when the membrane is used as a separator, the shrinkage rate should be as small as possible. Thermal shrinkage is a common problem, especially in the case of separators made of other plastic materials. The membranes and separators of the present invention exhibit little or minimal shrinkage at temperatures above 150 °C or higher. The shrinkage rate is calculated from the dimensional change: Shrinkage rate (%) = (L i - L f ) / L i × 100, where L i is the initial dimension and L f is the final dimension after exposure to high temperature. In one embodiment, the membranes or separators of the present disclosure made by a wet process have a longitudinal shrinkage rate of less than 15%, less than 10%, less than 7%, or less than 5% at 120 °C. In one embodiment, the membranes or separators of the present disclosure made by a wet process have a transverse shrinkage rate of less than 10%, less than 7%, less than 5%, or less than 2% at 120 °C.

[0079] The membranes or separators of the present disclosure preferably have excellent tensile strength properties. Tensile strength can be measured longitudinally and transversely and generally depends on the manufacturing process. Uniaxially oriented membranes or separators have tensile strength measurements in one direction, while biaxially oriented membranes or separators have tensile strength measurements in both directions. Tensile strength can be determined according to ASTM D88 - 00. Ideally, the membrane or separator has sufficient mechanical strength such that during battery assembly, necking or width narrowing during winding or unwinding can be minimized. In a preferred embodiment, the membranes or separators of the present disclosure have a longitudinal tensile strength greater than 1000 kg / cm 2 , greater than 1100 kg / cm 2 , greater than 1200 kg / cm 2 , or greater than 1400 kg / cm 2 . In other embodiments, the membranes or separators of the present disclosure can have a transverse tensile strength greater than 700 kg / cm 2 , greater than 750 kg / cm 2 , greater than 800 kg / cm 2 , or greater than 850 kg / cm 2 . The conductive membranes of the present disclosure also preferably have, when measured by cyclic voltammetry, a potential greater than 4 volts (versus Li 0 / Li + ), preferably greater than 4.5 volts (versus Li 0 / Li + ), more preferably greater than 5 volts (versus Li 0 / Li +) at a voltage of less than 0.1 mA / cm 2 of current density. In another embodiment, the conductive film of the present disclosure has a normalized current of less than 0.1 mA / cm 0 / Li + ) in a voltage range of 3 to 5 volts (relative to Li 0 / Li + ), for example, 4 to 5 volts (relative to Li 0 / Li + ) or 4.5 to 5 volts (relative to Li 2 / Li 0 / Li + ). In yet another embodiment, the conductive film of the present disclosure has a normalized current of less than 0.2 mA / cm 0 / Li + ) when the voltage is greater than 4.2 volts (relative to Li 0 / Li + ), for example, greater than 4.5 volts (relative to Li 0 / Li + ), greater than 4.7 volts (relative to Li 0 / Li + ), greater than 4.8 volts (relative to Li 2 / Li 0 / Li + ), for example, 4 to 5 volts (relative to Li 0 / Li + ) or 4.5 to 5 volts (relative to Li 0 / Li + ). In another embodiment, the conductive film has a normalized current of less than 0.2 mA / cm 2 in a voltage range of 3 to 5 volts (relative to Li

[0080] Those skilled in the art refer to the point at which current begins to flow unimpeded as the decomposition onset current. At this time, the polymer material constituting the film or diaphragm decomposes, which has an adverse effect on the integrity of the film and diaphragm and their practicality in the battery. In one aspect of the present disclosure, the decomposition onset current of the conductive film may be greater than 4.5 volts (relative to Li 0 / Li + ), for example, greater than 4.7 volts (relative to Li 0 / Li + ), greater than 4.8 volts (relative to Li 0 / Li + ), greater than 4.9 volts (relative to Li 0 / Li + ) or greater than 5 volts (relative to Li 0 / Li + ) and more preferably greater than about 6 volts (relative to Li 0 / Li + ) and most preferably greater than about 7 volts (relative to Li 0 / Li + ).

[0081] Separator membranes of the prior art suffer chemical and physical decomposition of the composition constituting the separator membrane at lower voltages. For example, conventional polyethylene oxide lithium solid polymer electrolytes (PEO) are considered stable only for 3.7 V (relative to Li 0 / Li + ). Conventional porous separator membranes impregnated with liquid electrolytes are considered stable for about 4.25 volts (relative to Li 0 / Li + ). Thus, the battery cannot be charged at voltages higher than the voltage at which the decomposition start current begins to flow without decomposing the electrolyte or the separator membrane. To increase the energy density of the battery, it is desirable to charge to increasingly higher voltages without decomposing the electrolyte and the separator membrane.

[0082] The conductive membranes of the present disclosure are made of a polymer blend composition comprising the polymers of the present invention and one or more metal salts (such as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)). When the start current of the polymer composition of the conductive membrane occurs at a higher voltage, the polymer blend composition and the resulting conductive membrane made therefrom are significantly more stable. This effect was confirmed when measuring and interpreting cyclic voltammetry (CV), an electrochemical analysis technique for measuring the current caused by an applied voltage. As the voltage increases, the current is measured, and if the polymer blend composition of the conductive membrane remains electrochemically stable, the change in current is relatively small. This continues until the decomposition start voltage is reached, at which point an unhindered increase in current can be clearly observed. For example, some embodiments of the present disclosure surprisingly and unexpectedly exhibit a relatively constant current up to about 5 V (relative to Li 0 / Li + ).

[0083] The synthesized polymers can form a wide variety of different morphologies depending on the intended application. In some aspects, for example, the polymers can form fibers (e.g., fiber webs) and / or membranes. To form fibers and / or membranes, as described above, the synthesized polymers can be spun into fibers, for example, by electrospinning or air jet spinning. For separator applications, it may be necessary to form a polymer membrane using the doctor blade casting method as described above.

[0084] When forming fibers and / or membranes, one or more additives can be introduced into the synthesized polymer. For example, the additives can include metal oxides, nitrides, borates, or lithium conductive ceramics. Specific examples of such additives can include silica, low-density lightweight lithium conductive ceramics (such as Li1+xAlxTi2-xP3O12 (LATP)), LLZO, clays (such as montmorillonite or attapulgite), zinc oxide, or boron nitride / vanadium nitride, etc.

[0085] Battery Applications

[0086] As described above, the polymers of the present disclosure can be incorporated into various aspects of solid-state batteries. Now referring to Figure 2 and Figure 3 , in addition to the high-energy density lithium solid anode 111 of the solid-state battery 100, embodiments of the solid separator 131 of the solid-state lithium-ion battery are also depicted. Referring to Figure 2 , the solid-state battery 100 includes a solid-state anode 111 having a fibrous framework solid electrolyte 112 and optionally containing the polymers of the present disclosure. The solid-state battery 100 can include metal ion deposits 120. The solid-state battery 100 further includes a cathode 113 having a solid cathode current collector 132. The solid separator 131 can be located between the anode 111 and the cathode 113, where one or more of them can contain the polymers of the present disclosure together or individually.

[0087] The solid-state anode 111 can be formed by one or more layers of solid electrolyte 112, and the solid electrolyte 112 can be formed by a fiber framework containing the polymers of the present disclosure. Generally, the solid-state anode 111 can be understood as a negative electrode or a reduction electrode, which releases electrons to the external circuit and oxidizes during the discharge process. The cathode 113 can be understood as a positive electrode or an oxidation electrode, which obtains electrons from the external circuit and reduces during the discharge process. In this embodiment, the solid-state anode 111 can be composed of the solid electrolyte 112, and the solid electrolyte 112 can be understood as an interconnected fiber framework. Ideally, the solid electrolyte contains a lithium salt dissolved in the dry polymer of the present disclosure as a solid solution. Of course, the solid electrolyte must be conductive to appropriate metal ions (usually lithium ions). The interconnected fiber framework of the solid-state anode 111 containing components made of the polymers of the present disclosure can have various properties and can be flexible or rigid. For a ceramic fiber framework, the ceramic can be used to provide structure or support for the solid-state anode 111 and the solid-state battery 100, and the ceramic fibers can be used or combined with the polymers of the present disclosure. The ceramic fibers provide conductivity for lithium ions, but since they do not provide conductivity for electrons, lithium metal cannot be deposited on the fibers. Instead, the lithium metal will plate at the interface between the lithium-conductive ceramic fibers and the current collector. Therefore, the plated lithium will fill the voids between the conductive fibers. The lithium metal at the metal ion deposit 120 can provide electronic conductivity for the solid-state battery 100, while the solid ceramic framework / skeleton can provide volume support, the surface layer of the metal ion deposit 120, and lithium ion conductivity.

[0088] One benefit of using the lithium-conductive ceramic fiber mats of the present disclosure is to inhibit the swelling and shrinkage caused by the plating and stripping of lithium metal during cycling. When using the fiber mats, the plating and stripping advantageously occur inside the fiber mat framework, thus preventing the swelling and shrinkage associated with many conventional solid-state batteries. In one embodiment, the polymers of the present disclosure are mixed or coated with ceramics to impart porosity and / or flexibility thereto. Thus, one method of combining, fabricating, "pre-lithiating", and / or operably joining the metal ion deposit 120 with the fiber framework of the solid electrolyte 112 is by injecting a partially molten lithium metal into the treated ceramic framework. Initially, it may only be necessary to inject a small amount of lithium metal into the pre-cell assembly of the solid-state anode 111. In this case, when only a small amount of lithium metal is injected into the pre-cell assembly of the solid-state anode 111, most or even all of the reversible lithium that gives the cell its capacity will come from the cathode 113 in the final assembly.

[0089] The lithium conductor portion of the solid anode 111 of the solid-state battery 100 can be a polymer framework in the solid electrolyte 112, where the polymer framework contains the polymers of the present disclosure. The polymer framework of the solid electrolyte 112 within the solid anode 111 can provide the additional advantage of flexibility. This can bring various benefits and trade-offs at the level of a single cell or the solid-state battery 100. The requirements for the polymer framework of the solid anode 111 and the materials deposited therein optionally include: (a) a melting point higher than that of lithium metal (about 180 °C); (b) non-conductivity of lithium ions; and (c) injecting a lithium-conductive material into the structure of the solid electrolyte 112, such as other conductive polymers with corresponding lithium salts (e.g., lithium bis(trifluoromethanesulfonyl)imide / LiC2F6NO4S2 / LiTFSI) or ceramic particles embedded in and / or on the surface of the polymers of the present disclosure. In such embodiments, there may be other components, manufacturing methods, and further variations, resulting in various benefits and trade-offs. These can include fiber mats extending throughout the solid anode 111 and the solid electrolyte 112. Additionally, while not all coatings for ceramic fiber frameworks are suitable for polymer or polymer fiber frameworks, and not all properties and characteristics of ceramic fiber frameworks can be directly applied to polymer or polymer fiber frameworks, some can be.

[0090] Now referring to Figure 3 , a solid separator 131 for a battery (e.g., a solid-state lithium-ion battery) is depicted. Broadly speaking, the solid separator 131 for a solid-state lithium-ion battery can be formed as one or more sheets, each sheet having a microstructure. The structure can include, but is not limited to, the primary polymer 320 of the present disclosure, which can be formed from the first monomer and the second monomer described herein (illustrated as the coarser of the two sets of long fibers throughout the solid separator 131). Although the polymers of the present disclosure preferably have sufficient structural integrity without further support, in some alternative embodiments, the structure can also include a structural polymer 330 (illustrated as the finer of the two sets of long fibers throughout the solid separator 131) and / or reinforcing additives 310 (illustrated as a set of circles throughout the solid separator 131). It should be understood that although each side of the solid separator 131 may have unique or different features, qualities, chemical compositions, etc., and / or combinations thereof, for the purposes of the present disclosure, the top 340 and the bottom 350 can be considered to have ambiguous features. That being said, if the top 340 can be operatively engaged with the cathode 113, then the bottom 350 will be operatively engaged with the anode 311. Although Figure 3 not drawn to scale and the microscopic appearance or structure of the solid separator 131 is not explicitly depicted, Figure 3 an exemplary illustration is depicted to further illustrate the use, structure, and formation of the solid separator 131. Additionally, those skilled in the art should understand Figure 3The cross-sectional properties shown are understood and may represent only a small fraction of the materials required for a single-cell solid-state lithium-ion battery. The thickness of the solid separator 131 is understood to be approximately uniform, but at the microscale, a gradual change in thickness can be significant. The solid separator 131 is understood to be very thin, with a high surface area and a low density. Other objective qualities of the solid separator 131 will be understood and elaborated upon below.

[0091] As Figure 3 shown, the optional structural polymer 330 can be repeated in the length, width, and depth of the solid separator 131 and is understood to be distributed approximately and / or uniformly throughout the solid separator 131. The properties of the solid separator 131 are (i) lithium ionic conductivity and (ii) electronic insulation. Another property that may be considered beneficial (although not critical) may be a low material density, which may be necessary to produce a high-energy-density cell. As mentioned above, the lowest-density solid materials are polymers, making the lithium-conducting polymers of the present disclosure excellent candidates for the solid separator 131 in order to provide a framework for the solid-state cell and endow it with the property of high energy density. The lithium ionic conductivity in polymers is determined by Li + coordination sites. Such groups can include ether oxygen, carbonate / salt oxygen, or silicon-based polymers (with similar functions), such as siloxanes. Other Li +The conductive sites can be nitrogen-based, phosphorus-based or sulfur-based, such as those found in polydopamine, polyimide, polyphosphazene or polysulfonate / salt. Preferably, the total thickness of the solid separator 131 should be less than 30 microns, such as less than or about 28 microns, less than or about 26 microns, less than or about 24 microns, less than or about 22 microns, less than or about 20 microns, less than or about 18 microns, less than or about 16 microns, less than or about 14 microns, less than or about 12 microns, less than or about 10 microns or less. The solid separator 131 should also be independent and stable in humid air. These requirements, in addition to being beneficial to the overall utility and function of the solid separator 131, can also promote the adoption of the solid separator 131 and solid-state batteries by battery manufacturers across different markets. By forming a composite material by mixing with inorganic materials (such as the reinforcing additive 310), its modulus of strength can be improved. In addition to the main polymer 320 and the structural polymer 330, it is desirable that these inorganic materials that can include the reinforcing additive 310 also have lithium conductivity and low density. Such inorganic additives that can include the reinforcing additive 310 can be clay, metal oxides, nitrides or lithium-conductive ceramics, such as lithium titanium aluminum phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphorus sulfur chloride (LSPSCl), lithium germanium phosphorus sulfide (LGPS), lithium-conductive halides, closo / nido borates, their analogues and / or their combinations. Electron-insulating carbon-based additives can also be used to form the reinforcing additive 310. Whether inorganic or carbon-based, the reinforcing additive 310 can be retained as a small part of the composite material while still being useful for its reinforcing purpose. An exemplary amount of the reinforcing additive 310 can be less than or about 10 wt%.

[0092] The method of combining the host polymer 320, the optional structural polymer 330, and the optional reinforcing additive 310, or the method of combining any two of them, may be crucial for influencing the overall utility, structure, function, and use of the solid separator 131. An example of the method of combining the host polymer 320, the structural polymer 330, and / or the reinforcing additive 310 may be electrospinning. This can be understood as a method of combining polymers and inorganic materials into a composite material or forming a polymer / inorganic composite material. In addition, the production of the solid separator 131 by electrospinning can be understood as producing a highly porous mat (i.e., a fibrous mat with a porosity > 90%), which can then be impregnated with a conductive polymer. Those skilled in the field of nonwoven material manufacturing can understand that electrospinning on a laboratory scale can generally be carried out by applying a high voltage between a metal syringe needle and a conductive plate. Electrospinning may be a more adaptable fiber spinning technique than traditional melt spinning. Electrospinning can be carried out via a room temperature process and can generate randomly arranged or aligned fibrous mats according to the desired structure of the fibrous mat. The resulting fibrous mat produced by this process can be kept exposed to ambient air at room temperature while remaining non-reactive. If the needle electrospinning method is adopted, even hollow fibers can be obtained using coaxial needles. This method can even further reduce the weight of the solid separator 131. Although there are currently problems with scaling up this well-known laboratory process, following the same principle, a viscous colloid can be modified to spin fibers through a rotating conductive helix under voltage without using a needle. Using the modified viscous colloid to spin through a rotating conductive helix under voltage without using a needle may be a scalable process. Utilizing the modified viscous colloid technology may be important for the scalable production of the host polymer 320, the structural polymer 330, and the reinforcing additive 310 (or the combination of any two of them) to form the solid separator 131 in a porous solid mat.

[0093] A method of combining a host polymer 320, a structural polymer 330, and a reinforcing additive 310 (or a combination of any two of those) may further include doctor blading to form a solid separator 131. By doctor blading a polymer, inorganic, and / or lithium salt mixture, one skilled in the art can form a robust, porous fibrous mat having lightweight properties as described herein, suitable for use as the solid separator 131. Doctor blading can have further benefits in that it is itself a scalable process and is also a conventional process known in the battery industry. For example, almost all battery electrodes can be assembled by this technique. The doctor blading method of such mixtures can provide further benefits in solid separators 131 comprising polymer blends, achieving the required strength at the required thickness. However, if the main component of the solid separator 131 is a polymer composition and if that polymer composition is also self-standing, it may be challenging to obtain a large-area solid separator 131 that is thin (e.g., less than or about 30 microns). Instead, this method may be more suitable for a complete layered cell assembly procedure where the solid separator 131 is laminated on top of the electrodes to form a top-down fully internal multi-cell battery assembly. In this case, since the assembly can be carried out simultaneously with the fabrication of the solid separator 131, the above self-standing requirement is not necessary. Some materials that can be used as components of the doctor blading slurry to fabricate the solid separator 131 include but are not limited to fumed silica (inorganic additive) + G4 (tetraethylene glycol dimethyl ether, solvent) and / or LiTFSA (lithium salt), LiBOB, LiTFSI, LiBF2(C2O4), LiBF2(C2O4), C2O4Li2, CF3CO2Li, C6H5COOLi, other lithium salts, analogs thereof, and / or combinations thereof.

[0094] In addition to forming the solid separator 131 by electrospinning or doctor blading the host polymer 320, the structural polymer 330, and the reinforcing additive 310 or a combination of any two of those, it may be further important to provide an interfacial coating (or bonding coating) at the interface with the anode or cathode. Since it may be desirable to maximize the lithium ionic conductivity across the thin (e.g., less than or about 30 microns) solid separator 131, additional treatment of the top 340 and / or bottom 350 of the solid separator 131 may be required to allow the anode and cathode to be so close even in the presence of the solid separator 131. In other words, the interface between the anode and / or cathode and the solid separator 131 may require additional treatment to ensure the long-term operation, durability, and sustainability of the solid-state battery 100. This can be a serious issue, especially at the interface with the exposed lithium metal of the solid-state anode 111. The interfacial coating can generally be applied, formed, or otherwise located at the top 340 and / or bottom 350. Exemplary coatings that can stabilize and facilitate this interface include, but are not limited to, graphite / graphene (i.e., carbon), nitrides / borates (e.g., boron nitride, MgB2, Cu3N), metal alloys (e.g., an Al coating formed from an AlX3 or Al(NO3)3 salt dissolved in solution, an In coating formed from In(TFSI)3, InF3, In(NO3)3, or a salt thereof dissolved in solution), sulfur (e.g., Li2S+S, LPS), or fluoroethylene carbonate (FEC) (i.e., fluoroethylene carbonate, a cathode stabilizer additive).

[0095] Components prepared or constructed according to embodiments of the present invention can have enhanced electrical properties. For example, a battery can be characterized in that its capacity is greater than or about 1200 mAh / g, e.g., greater than or about 1225 mAh / g, greater than or about 1250 mAh / g, greater than or about 1275 mAh / g, greater than or about 1300 mAh / g, greater than or about 1325 mAh / g, greater than or about 1350 mAh / g, greater than or about 1375 mAh / g, greater than or about 1400 mAh / g or higher. The battery can be characterized in that its energy density is greater than or about 500 Wh / kg, e.g., greater than or about 525 Wh / kg, greater than or about 550 Wh / kg, greater than or about 575 Wh / kg, greater than or about 600 Wh / kg, greater than or about 625 Wh / kg, greater than or about 650 Wh / kg or higher.

[0096] In addition, in one embodiment, a separator made of a conductive film made of the polymers of the present disclosure may be characterized by an ionic conductivity greater than 0.01 mS / cm, as described above in connection with the disclosed polymers, and may be characterized by an ionic conductivity greater than 0.05 mS / cm, greater than 0.10 mS / cm, greater than 0.15 mS / cm, or greater than 0.20 mS / cm. In terms of range, the separator optionally has an ionic conductivity of 0.01 to 0.3 mS / cm, such as 0.05 to 0.25 mS / cm, or 0.1 to 0.25 mS / cm.

[0097] Accordingly, in one embodiment, the present disclosure provides a solid-state battery comprising: a solid-state anode; a solid-state cathode; and a solid-state metal-ion conductive separator sandwiched between the anode and the cathode; wherein at least one of the solid-state anode and the solid-state separator comprises a component having a copolymer composition containing a metal salt as described above.

[0098] In one embodiment, the present disclosure provides a solid-state lithium battery comprising a solid-state anode capable of intercalating and deintercalating lithium ions; a solid-state cathode capable of intercalating and deintercalating lithium ions; and a solid-state lithium-ion conductive separator sandwiched between the anode and the cathode; wherein at least one of the solid-state anode, the solid-state cathode, and the solid-state separator comprises a component having a copolymer composition containing a lithium salt as described above.

[0099] In one aspect of the solid-state lithium battery embodiment, the solid-state lithium-ion conductive separator comprises the composition, wherein the lithium salt comprises one or more selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi. The solid-state lithium-ion conductive separator may further comprise at least one of the following: (i) a polymer different from the copolymer and / or (ii) an additive selected from clays, metal oxides, metal nitrides, and lithium-conductive ceramics. The solid-state lithium-ion conductive separator may comprise a lithium-conductive ceramic selected from the following materials: lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphorus sulfur chloride (LSPSCl), lithium germanium phosphorus sulfide (LGPS), lithium-conductive halides, closo-borates, and nido-borates. The solid-state lithium-ion conductive separator may be in the form of a film having a thickness of less than 30 microns, and wherein the ionic conductivity of the film is 0.05 mS / cm or higher.

[0100] In another aspect of the solid-state lithium-ion battery embodiment, the solid anode comprises the composition, and the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0101] In another aspect of the solid-state lithium-ion battery embodiment, the solid cathode comprises the composition, and the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0102] In view of the above description, it should be recognized that the optimal dimensional relationships include variations in size, material, shape, form, location, function and mode of operation, assembly, anode / cathode / battery container type, connection type, and use, all of which are intended to be covered in the present disclosure. It is contemplated herein that the solid separator 131 and the various components and assemblies described herein may include various overall dimensions as well as corresponding dimensions of the individual components, including but not limited to the solid anode 111, solid electrolyte 112, metal ion deposit 120, cathode 312, cathode current collector 132, their analogs, and / or their combinations. In fact, the individual components and assemblies of the solid-state battery 100 may vary in terms of size, shape, etc. during their standard operation. The description of the solid separator 131 herein mentions its benefits for electric vehicles and other electronic devices, but the present invention is not limited thereto. The solid separator 131 of the solid-state lithium-ion battery of the present disclosure and the battery made therefrom can be used to power other vehicles, computers, enterprises, residences, industrial facilities, consumer and portable electronic devices, hospitals, factories, warehouses, government facilities, data centers, emergency backup power supplies, aerospace, space travel, robots, drones, their analogs, and / or their combinations. The chemical formulas, metals, atomic and molecular compositions (“disclosed formulas”) provided herein are merely examples. Those skilled in the art should understand that variations of the disclosed formulas may present some trade-offs for the solid separator 131 of the solid-state lithium-ion battery of the present disclosure, and similar advantages to those of the solid separator 131 of the solid-state lithium-ion battery of the present disclosure can be achieved through substitution. In addition, due to differences in materials and manufacturing techniques (including but not limited to polymers, alloys, metals, assembly, tabbing, welding, atmospheric components, etc. and their combinations), various factors need to be considered in battery manufacturing. However, still, although various methods of manufacturing and assembling batteries have been contemplated to achieve a greater electrical storage capacity per unit mass (energy density), provide a high working current, increase the durability and life of the battery, increase the range of reliable operation of the battery, provide a safer battery, and a more efficient production method, the present disclosure is not limited to the specific components, benefits listed and described herein, and / or the manufacturing methods listed herein.

[0103] The present invention will be further understood in conjunction with the following non-limiting examples. In the tables below, comparative examples are denoted by “CE” hereinafter, and those containing M3 are GLA or GMA. Example CE69 corresponds to Example 1 of CN110518282B. This example exhibited a very low yield (14 wt.%), and a low viscosity was observed, reflecting a low molecular weight. Example

[0104] The following table lists various examples of polymers formed for use in the separator, such as the main polymer 320 in the solid separator 131. Table 1 lists the examples and lists the first monomer (M1), the second monomer (M2), and (if included) the third monomer (M3). The polymers were prepared according to four synthetic schemes: Process A, Process B, Process C, and Process D, as described below. All examples marked "CE" in Tables 1 and 2 are comparative examples.

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] *Unless otherwise specified, all processes were carried out at 60 °C. ND = Not determined.

[0111] Key information on monomer abbreviations: vinylene carbonate (VC), 4-vinyl-1,3-dioxolan-2-one (ethylene carbonate ethyl ester or VEC), poly(ethylene glycol) methyl ether methacrylate MW500 (PEGMA500), poly(ethylene glycol) methyl ether methacrylate MW360 (PEGMA360), poly(ethylene glycol) methyl ether methacrylate MW1000 (PEGMA1000), dimethyl vinylphosphonate (DMVP), butyl cyanoacrylate (BCA), n-butyl acrylate (NBA), pentafluoropropyl methacrylate (PFMA), glycidyl acrylate (GLA), glycidyl methacrylate (GMA), N-methylmaleimide (NMM), and dimethyl vinylphosphonate (DMVP). VAZO52 refers to 2,2'-azobis(2,4-dimethylvaleronitrile).

[0112] Process A

[0113] A 25 mL reaction vial was equipped with a stir bar and charged with the first monomer (M1), the second monomer (M2), and (when indicated) the third monomer (M3), a solvent, and an initiator under argon. The mixture was bubbled with argon and then sealed. The reaction vial was placed in a heating block with the temperature set within the range shown in Table 1. Initiation was indicated by the formation of bubbles. The vial was then stirred at the temperature shown in Table 1 for the corresponding time. A grayish-white viscous solution was obtained and poured into about 250 mL of stirred MeOH to form long polymer filaments. The supernatant was decanted, the product was washed with MeOH, and then ground with MeOH for 24 h. The MeOH was decanted and the grinding was repeated. The separated product was then dried under vacuum (1 torr) at 40 °C for 2 days to give a grayish-white polymeric product filament.

[0114] Process B

[0115] A 500 mL reaction vessel was equipped with an overhead stirrer and a nitrogen inlet / outlet and purged with nitrogen. Under nitrogen, the first monomer (M1), the second monomer (M2), (when indicated) the third monomer (M3), a solvent (99.9% anhydrous solvent, 80 mL), and an initiator were added to the flask to give a clear solution. The flask was covered with aluminum foil to protect from light and then heated in an oil bath to the temperature shown in Table 1. After the time shown in Table 1, heating of the reaction was stopped to give a very viscous solution. A 5 L reaction vessel was equipped with a stir bar, a nitrogen inlet, and a addition funnel and charged with 2.5 L of MeOH. The viscous polymer solution was then slowly added to the stirred MeOH through the addition funnel. A white precipitate formed. The supernatant was decanted, the product was ground with MeOH for 24 h. The MeOH was decanted. This was repeated. The separated product was then dried under vacuum (1 torr) at 40 °C for 2 days to give a grayish-white polymeric filament.

[0116] Process C

[0117] Equip a 500 mL reaction flask with a stir bar, a gas inlet / outlet, and an oil bath. Purge the flask with argon, add VC, hexane, and an initiator, and heat to the temperature shown in Table 1. Weigh the first monomer (M1), the second monomer (M2), and (when indicated) the third monomer (M3), and combine them in a vial for batch addition. After 30 minutes, add 6 mL of the monomer solution and stir the reaction at the temperature shown in Table 1 for 16 hours. After 16 hours, a gel forms below the hexane layer. Add an additional 10 mL of the monomer mixture and continue the reaction for an additional 24 hours. Then add the remaining monomer mixture and continue the reaction, monitoring with NMR. After 4 days, a small amount of unreacted M1 remains. Add an additional dose of the initiator and continue the reaction overnight to obtain a translucent solid. Cool the reaction to room temperature, decant the hexane layer, break up the solid, and wash it several times with hexane. Transfer the solid to a 1 L round-bottom flask and dry it by rotary evaporation at 60 °C, then dry it in a vacuum oven at 60 °C for 2 days.

[0118] Process D

[0119] Equip a 20 mL reaction vial with a stir bar and add the first monomer, the second monomer, a solvent, and an initiator under argon protection. Bubble the mixture with argon and then seal it. Place the reaction vial in a heating block at the temperature shown in Table 1. Monitor the reaction progress by NMR until the first monomer is depleted or the reaction stops. After the reaction is complete, a grayish-white viscous solution is obtained, which is poured into 250 mL of stirred MeOH to form long polymer filaments. Decant the supernatant, wash the product with MeOH, and then grind it with MeOH for 24 hours. Decant the MeOH and repeat the grinding. Then dry the separated product in vacuo (1 torr) at 40 °C for 2 days to obtain grayish-white polymer product filaments.

[0120] Table 1 above shows that the monomers used in the present disclosure unexpectedly result in a polymerization yield much higher than that of the comparative examples. This generally means a higher monomer incorporation rate and a more uniform polymer. Without being bound by theory, we believe that the polymers prepared from monomers containing glycidyl groups (ether bonds) in the comparative examples dissociate in the presence of a solvent, thereby generating unfavorable low molecular weight polymers. This effect makes it more difficult to prepare membranes useful herein and may have a harmful impact on battery applications, especially high-voltage battery applications.

[0121] Gel permeation chromatography (GPC) molecular weight determination, also known as size exclusion chromatography (SEC) testing, was performed using an Agilent 1100 HPLC equipped with a thermostatic column oven, a refractive index detector, and a variable wavelength ultraviolet-visible light detector.

[0122] The chromatographic column used for separation was an Agilent Plgel Mixed-C column (5 μm, 300 mm X 7.5 mm), with a nominal linear molar mass separation range of 200 - 2,000,000 g / mol. These columns were packed with a stationary phase containing gel particles of approximately 5 μm, which consisted of a highly cross-linked polystyrene / divinylbenzene matrix. These columns were organic GPC columns and were compatible with most organic mobile phase solvents. Two identical columns were connected in series to maximize the overall system resolution.

[0123] Part of the sample was transferred to a glass vial equipped with a PTFE-lined metal cap using a spatula. The sample was then immersed in a mobile phase containing dimethyl sulfoxide (DMSO) and 0.1% lithium bromide to a concentration of approximately 2 mg / mL. The sample was then heated in DMSO at 35 °C for approximately 20 hours with gentle stirring.

[0124] The Mw and dispersity of the polymers of Examples 23, 31, 50, and 53 were tested. Their respective molecular weights (Mw) were 50,100 Da, 4,940 Da, 112,461 Da, and 81,500 Da, and their respective dispersities were 3.3, 1.6, and 3.9. Their Mn values were 15,600 Da, 3,060 Da, and 20,800 Da respectively. Their Mz values were 97,000 Da, 8,340 Da, and 162,000 Da. The surprising effect was that the molecular weight of the polymers of the present disclosure did not decrease after contact with the solvent (in this case DMSO). The data collected by refractive index (RI) detection was used to characterize the molecular weight and dispersity of the samples. The data was analyzed using Agilent GPC / SEC software version 2.2. A calibration curve was created that included narrow band polyethylene oxide / ethylene glycol standards with a molar mass of approximately 200 to 1,500,000 g / mol. Since the two highest molar mass standards and one of the lowest molar mass standards were outside the exclusion and permeation limits of the column, they were not used; however, the calibration curve was linear (r2 = 0.9947) and was used to extrapolate down to the permeation limit (system peak, elution time of approximately 16.7 minutes).

[0125] The molar mass moments and dispersity (D) were calculated using Agilent GPC / SEC software (version 2.2) according to the following formulas:

[0126]

[0127] Among them, Mn is the number-average molar mass moment (the number of molecules above and below this molar mass in the distribution is equal), Mw is the weight-average molar mass moment (the molecular weights of the molecules above and below this molar mass in the distribution are equal), and Mz is the higher-order z-average molar mass moment, which is more sensitive to polymers with higher molar masses in the distribution. Dispersity Characterizes the width of the molar mass distribution. The larger it is, the wider the distribution. For a uniform compound,

[0128] Film Formation

[0129] The obtained polymer was dissolved in a solvent and cast by a doctor blade. The parameters used for film formation are listed in Table 2 below. The thickness of the obtained polymer was also measured as follows and reported in Table 2. The polymers determined in the table were dissolved in DMSO or NMP respectively at a concentration of 15% by mass. According to this process, 1 g of the polymer can be dissolved in about 6 g of DMSO. A metal salt, specifically lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), was added to the solution in the proportion shown in Table 2. Then the obtained mixed solution was cast onto aluminum foil with a wet gap of 82 - 100 μm. The cast solution was dried in a convection oven at 40 °C for 3 - 12 hours to obtain a film. The obtained film was further dried in a vacuum oven at 40 °C for 12 hours. The final film was imprinted into a button cell with an area of 1.327 square centimeters for further tests, such as conductivity and thickness tests. At the same time, it was observed whether the film had self-supportability.

[0130] Conductivity

[0131] According to the electrochemical impedance spectroscopy (EIS) described below, the conductivity of the selected examples was measured and reported in Table 2. When the initial current of the polymer composition of the conductive film occurs at a higher voltage, the polymer blend composition and the obtained conductive film are significantly more stable. This effect was confirmed when measured and interpreted by cyclic voltammetry (CV), which is an electrochemical potential measurement method used to measure the current caused by an applied voltage. As the voltage increased, the current was measured. Surprisingly and unexpectedly, high stability was observed at high voltages, which was reflected in the stable normalized current at high potentials until the current increased significantly. For some examples (such as Example 50), stability was also observed at voltages up to 5.0 V (relative to Li + / Li).

[0132] The methods, systems, devices, diagrams, and tables discussed in this document are merely examples. Various configurations may omit, replace, or add various procedures or components as needed. For example, in alternative configurations, the methods may be executed in an order different from the described order, and / or individual stages may be added, omitted, and / or combined. Additionally, features described for certain configurations may be combined in various other configurations. Different aspects and elements of the configurations may be combined in a similar manner. Moreover, technology is constantly evolving, so many elements are merely examples and do not limit the scope of the present disclosure or the claims. Additionally, the techniques discussed herein may provide different results depending on different types of context-aware classifiers.

[0133]

[0134]

[0135]

[0136] **These examples exhibit high electrical conductivity due to the very low molecular weight of the resulting polymer. The film appears to be plasticized with very short chains and is in a quasi-solid state, similar to wax. The film cannot be lifted like a free-standing film (the liftability of the film corresponds to a significant increase in molecular weight). As described above, polymers with a greater molecular weight are desired, such that less polymer is required, resulting in a higher total salt content and a higher "true" dry electrical conductivity.

[0137] Embodiments

[0138] Embodiment 1. A copolymer comprising the following as copolymer units:

[0139] Vinylene carbonate compound as a first monomer; and at least one additional monomer different from the first monomer and copolymerizable with the first monomer, provided that the at least one additional monomer does not contain a glycidyl group; wherein the molar ratio of the first monomer to the at least one additional monomer is from 4:1 to 99:1.

[0140] Embodiment 2. The copolymer according to Embodiment 1, wherein the first monomer is vinylene carbonate.

[0141] Embodiment 3. The copolymer according to Embodiment 1, wherein the first monomer is a derivative or analogue of vinylene carbonate.

[0142] Embodiment 4. The copolymer according to any one of the foregoing embodiments, wherein the at least one additional monomer is selected from poly(ethylene glycol) methacrylate (PEGMA), 1,3-propane sultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylene carbonate (VEC), dimethyl vinylphosphonate (DMVP), maleic anhydride (MA), diethyl vinylphosphonate (DEVP), diethyl allylphosphonate (DEAP), or N-vinylpyrrolidone (NVP), N-methylmaleimide, vinyl sulfite, vinylidene sulfite, vinyl vinylsulfite, or butadiene sulfone, vinylsulfonic acid (VSA), N,N-dimethylvinylsulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphospholane 2-oxide, metal salts of vinylsulfonic acid, metal salts of vinylphosphonic acid, metal salts of fluoro(vinyl)phosphinic acid, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metal salts of trifluoro(vinyl)boronic acid, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metal salts of 2-fluoro-2-vinyl-1,3,2-dioxaborolane-4,5-dione.

[0143] Embodiment 5. The copolymer according to any one of Embodiments 1-4, wherein the at least one additional monomer comprises two different additional monomers, each additional monomer being selected from poly(ethylene glycol) methacrylate (PEGMA), 1,3-propane sultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylene carbonate (VEC), dimethyl vinylphosphonate (DMVP), maleic anhydride (MA), diethyl vinylphosphonate (DEVP), diethyl allylphosphonate (DEAP), or N-vinylpyrrolidone (NVP), N-methylmaleimide, vinyl sulfite, vinylidene sulfite, vinyl vinylsulfite, or butadiene sulfone, vinylsulfonic acid (VSA), N,N-dimethylvinylsulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphospholane 2-oxide, metal salts of vinylsulfonic acid, metal salts of vinylphosphonic acid, metal salts of fluoro(vinyl)phosphinic acid, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metal salts of trifluoro(vinyl)boronic acid, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metal salts of 2-fluoro-2-vinyl-1,3,2-dioxaborolane-4,5-dione.

[0144] Embodiment 6. The copolymer according to any one of Embodiments 1-4, wherein the at least one additional monomer is 2,2,3,3,3-pentafluoropropyl methacrylate (PFMA), 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, or 2,2,3,3-tetrafluoropropyl methacrylate.

[0145] Embodiment 7. The copolymer according to any one of the preceding embodiments, wherein the copolymer is uncrosslinked.

[0146] Embodiment 8. The copolymer according to any one of the preceding embodiments, wherein the copolymer has a molecular weight greater than 50,000 Da and a density of 0.5 g / cm 3 to 2.5 g / cm 3 .

[0147] Embodiment 9. The copolymer according to any one of the preceding embodiments, wherein the copolymer has a melting point of 200 °C or higher.

[0148] Embodiment 10. The copolymer according to any one of Embodiments 1-8, wherein the copolymer does not exhibit a melting point and has an oxidation point of 350 °C or higher.

[0149] Embodiment 11. The copolymer according to any one of the preceding embodiments, wherein the copolymer has a molecular weight greater than 80,000 Da.

[0150] Embodiment 12. The copolymer according to any one of the preceding embodiments, provided that the at least one additional monomer does not contain an epoxy group and is not formed from a compound containing an epoxy group.

[0151] Embodiment 13. A composition comprising: the copolymer according to any one of the preceding embodiments; and a metal salt.

[0152] Embodiment 14. The composition according to Embodiment 13, wherein the metal salt comprises metal ions selected from alkali metals, alkaline earth metals, aluminum, and zinc.

[0153] Embodiment 15. The composition according to Embodiment 13, wherein the metal salt is a lithium salt.

[0154] Embodiment 16. The composition according to Embodiment 15, wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0155] Embodiment 17. The composition according to any one of Embodiments 13-16, wherein the ionic conductivity of the composition at 25 °C is 0.01 mS / cm or higher as measured by electrochemical impedance spectroscopy.

[0156] Embodiment 18. The composition according to any one of Embodiments 13-17, wherein the decomposition start current of the composition is 4.5 V or higher with respect to Li 0 / Li + .

[0157] Embodiment 19. The composition according to any one of Embodiments 13-18, wherein the composition has a lithium salt content of 20 wt% to 80 wt% based on the total weight of the composition.

[0158] Embodiment 20. A membrane, filament, nonwoven web or woven fabric comprising the composition according to any one of Embodiments 13-19.

[0159] Embodiment 21. A solid-state battery, comprising: a solid-state anode;

[0160] a solid-state cathode; and a solid-state metal ion conductive separator sandwiched between the solid-state anode and the solid-state cathode; wherein at least one of the solid-state anode and the solid-state metal ion conductive separator comprises a component having the composition according to any one of Embodiments 13-19.

[0161] Embodiment 22. A solid-state lithium-ion battery, comprising: a solid-state anode capable of intercalating and deintercalating lithium ions; a solid-state cathode capable of intercalating and deintercalating lithium ions; and a solid-state lithium-ion conductive separator sandwiched between the anode and the cathode; wherein at least one of the solid-state anode, the solid-state cathode and the solid-state separator comprises a component having the composition according to Embodiment 15.

[0162] Embodiment 23. The solid-state lithium-ion battery according to Embodiment 22, wherein the solid-state lithium-ion conductive separator comprises the composition, and wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li and C6H5COOLi.

[0163] Embodiment 24. The solid-state lithium-ion battery according to Embodiment 22 or Embodiment 23, wherein the solid-state lithium-ion conductive separator further comprises at least one of the following: (i) a polymer different from the copolymer, and (ii) an additive selected from clay, metal oxide, metal nitride and lithium conductive ceramic.

[0164] Embodiment 25. The solid-state lithium-ion battery according to any one of Embodiments 22-24, wherein the solid-state lithium-ion conductive separator comprises a lithium-conductive ceramic, and wherein the lithium-conductive ceramic is selected from lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphorus sulfur chloride (LSPSCl), lithium germanium phosphorus sulfide (LGPS), lithium-conductive halides, closo-borates, and nido-borates.

[0165] Embodiment 26. The solid-state lithium-ion battery according to any one of Embodiments 22-25, wherein the solid-state lithium-ion conductive separator is in the form of a film having a thickness of less than 30 microns, and wherein the ionic conductivity of the film is 0.05 mS / cm or higher.

[0166] Embodiment 27. The solid-state lithium-ion battery according to Embodiment 22, wherein the solid anode comprises the composition, and wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0167] Embodiment 28. The solid-state lithium-ion battery according to Embodiment 22, wherein the solid cathode comprises the composition, and wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0168] Embodiment 29. The solid-state lithium-ion battery according to any one of Embodiments 22-28, provided that the at least one additional monomer does not contain an epoxy group and is not formed from a compound containing an epoxy group.

[0169] Embodiment 30. A method for preparing the copolymer according to any one of Embodiments 1-12, comprising: dissolving a vinylene carbonate compound in a solvent; contacting at least one additional monomer with the vinylene carbonate compound and a polymerization initiator in the solvent under reaction conditions sufficient to copolymerize the vinylene carbonate compound with the at least one additional monomer, thereby obtaining the copolymer in a reaction mixture; precipitating the copolymer from the reaction mixture under conditions effective to precipitate the polymer; and separating the copolymer from the reaction mixture.

[0170] Embodiment 31. The method according to Embodiment 30, wherein the solvent is dimethyl sulfoxide, tetrahydrofuran, or N-methyl-2-pyrrolidone.

[0171] Embodiment 32. The method according to Embodiment 30 or Embodiment 31, wherein the polymerization initiator is 2,2'-azobis(2,4-dimethylvaleronitrile).

[0172] Embodiment 33. The method according to any one of Embodiments 30 - 32, wherein the reaction conditions sufficient to copolymerize the vinylene carbonate compound with at least one additional monomer include a temperature of 40°C to 100°C.

[0173] Embodiment 34. The method according to any one of Embodiments 30 - 33, wherein the copolymer yield of the method is greater than 50%.

[0174] Embodiment 35. A film comprising a polymer, the polymer comprising a first monomer of vinylene carbonate and a second monomer different from the first monomer and not having a glycidyl group; wherein the molar ratio of the first monomer to the at least one additional monomer is from 4:1 to 99:1.

[0175] Embodiment 36. The film according to Embodiment 35, further comprising a metal salt, wherein the thickness of the film is less than 30 microns, and the ionic conductivity of the film is 0.05 mS / cm or greater.

[0176] Embodiment 37. A separator comprising the conductive film according to Embodiment 36.

[0177] Embodiment 38. A conductive layer in an electrode, comprising the conductive film according to Embodiment 36.

[0178] Although the exemplary and presently preferred embodiments of the disclosed methods, separators, and batteries have been described in detail herein, it should be understood that the inventive concept can be embodied and used in other various ways, and the appended claims are intended to be construed to include such variations, subject to the limitations of the prior art.

[0179] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly or conventionally understood. The articles "a" and "an" as used herein refer to one or more (i.e., at least one) grammatical objects of the article. For example, "element" means one or more than one element. When the terms "about" and / or "approximately" are used herein in reference to a measurable value (such as an amount, a time period, etc.), they include a deviation of ±20%, ±10%, ±5%, or +0.1% relative to the specified value, since such deviations are applicable to the systems, devices, circuits, methods, and other implementations described herein. When the terms "substantially" are used herein in reference to a measurable value (such as an amount, a time period, a physical property (such as frequency), etc.), they also include a deviation of ±20%, ±10%, ±5%, or +0.1% relative to the specified value, since such deviations are applicable to the systems, devices, circuits, methods, and other implementations described herein. When a claim element is described as "selected from" a list of components, the element can be selected from any combination of one or more of these alternative components.

[0180] When a numerical range is provided, it is understood that each intervening value (to the smallest fraction of the lower limit unit) between the upper and lower limits of the range is also specifically disclosed, unless the context clearly dictates otherwise. Any value or intervening value specified within the stated range and any other specified value or intervening value within the stated range form a narrower range that is also covered. The upper and lower limits of these smaller ranges can independently be included or excluded from the range, and each range in which any one limit, neither limit, or both limits are included within the smaller range is also covered in the present technology, except for the limits specifically excluded from the stated range. When the stated range includes one or both limits, ranges excluding one or both of those included limits are also included.

[0181] As used herein (including in the claims), "and" when used in a list of items beginning with "at least one" or "one or more" means that any combination of the listed items can be used. For example, a list of "at least one of A, B, and C" includes any combination of A or B or C or AB or AC or BC and / or ABC (i.e., A, B, and C). Additionally, if the items A, B, or C may occur or be used more than once, multiple uses of A, B, and / or C can form part of the intended combination. For example, a list of "at least one of A, B, and C" can also include AA, AAB, AAA, BB, etc.

Claims

1. A copolymer comprising the following as copolymer units: Vinylene carbonate compound as a first monomer; and At least one additional monomer different from the first monomer and copolymerizable with the first monomer, provided that the at least one additional monomer does not contain a glycidyl group; Wherein the molar ratio of the first monomer to the at least one additional monomer is from 4:1 to 99:

1.

2. The copolymer of claim 1, wherein the first monomer is vinylene carbonate.

3. The copolymer of claim 1, wherein the first monomer is a derivative or analog of vinylene carbonate.

4. The copolymer of any one of the preceding claims, wherein the at least one additional monomer is selected from poly(ethylene glycol) methacrylate (PEGMA), 1,3 - propanesultone (PES), bis(2,2,2 - trifluoroethyl) maleate (TFM), vinylethylene carbonate (VEC), dimethyl vinylphosphonate (DMVP), maleic anhydride (MA), diethyl vinylphosphonate (DEVP), diethyl allylphosphonate (DEAP), or N - vinylpyrrolidone (NVP), N - methylmaleimide, vinylene sulfate, vinylene sulfite, ethylene vinylene sulfite, or butadiene sulfone, vinylsulfonic acid (VSA), N,N - dimethylvinylsulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2 - vinyl - 1,3,2 - dioxaphospholane - 2 - oxide, metal salts of vinylsulfonic acid, metal salts of vinylphosphonic acid, metal salts of fluoro(vinyl)phosphinic acid, 1 - vinylpyrrolidine - 2,5 - dione, vinylboronic acid, metal salts of trifluoro(vinyl)boronic acid, 2 - vinyl - 1,3,2 - dioxaborolane - 4,5 - dione, and metal salts of 2 - fluoro - 2 - vinyl - 1,3,2 - dioxaborolane - 4,5 - dione.

5. The copolymer of any one of claims 1-4, wherein the at least one additional monomer comprises two different additional monomers, each additional monomer being selected from poly(ethylene glycol) methacrylate (PEGMA), 1,3-propane sultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylene carbonate (VEC), dimethyl vinylphosphonate (DMVP), maleic anhydride (MA), diethyl vinylphosphonate (DEVP), diethyl allylphosphonate (DEAP), or N-vinylpyrrolidone (NVP), N-methylmaleimide, vinylene sulfate, vinylene sulfite, ethylene vinylene sulfite, or butadiene sulfone, vinylsulfonic acid (VSA), N,N-dimethylvinylsulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphospholane-2-oxide, metal salts of vinylsulfonic acid, metal salts of vinylphosphonic acid, metal salts of fluoro(vinyl)phosphinic acid, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metal salts of trifluoro(vinyl)boronic acid, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metal salts of 2-fluoro-2-vinyl-1,3,2-dioxaborolane-4,5-dione.

6. The copolymer of any one of claims 1-4, wherein the at least one additional monomer is 2,2,3,3,3-pentafluoropropyl methacrylate (PFMA), 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, or 2,2,3,3-tetrafluoropropyl methacrylate.

7. The copolymer of any one of the preceding claims, wherein the copolymer is uncrosslinked.

8. The copolymer of any one of the preceding claims, wherein the copolymer has a molecular weight greater than 50,000 Da and a density of from 0.5 g / cm 3 to 2.5 g / cm 3 .

9. The copolymer of any one of the preceding claims, wherein the copolymer has a melting point of 200 °C or higher.

10. The copolymer of any one of claims 1-8, wherein the copolymer does not exhibit a melting point and has an oxidation point of 350 °C or higher.

11. The copolymer of any one of the preceding claims, wherein the copolymer has a molecular weight greater than 80,000 Da.

12. The copolymer of any one of the preceding claims, provided that the at least one additional monomer does not contain an epoxy group and is not formed from a compound containing an epoxy group.

13. A composition comprising: the copolymer of any one of the preceding claims; and a metal salt.

14. The composition of claim 13, wherein the metal salt comprises metal ions selected from alkali metals, alkaline earth metals, aluminum, and zinc.

15. The composition of claim 13, wherein the metal salt is a lithium salt.

16. The composition of claim 15, wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

17. The composition according to any one of claims 13 - 16, wherein the ionic conductivity of the composition at 25 °C, measured by electrochemical impedance spectroscopy, is 0.01 mS / cm or higher.

18. The composition according to any one of claims 13 - 17, wherein the decomposition starting current of the composition is 4.5 V or higher relative to Li 0 / Li + or higher.

19. The composition according to any one of claims 13 - 18, wherein the composition has a lithium salt content of 20 wt% to 80 wt% based on the total weight of the composition.

20. A membrane, filament, non - woven fabric or woven fabric comprising the composition according to any one of claims 13 - 19.

21. A solid - state battery, comprising: A solid - state anode; A solid - state cathode; and A solid - state metal - ion - conducting separator sandwiched between the solid - state anode and the solid - state cathode; Wherein at least one of the solid - state anode and the solid - state metal - ion - conducting separator comprises a component having the composition according to any one of claims 13 - 19.

22. A solid - state lithium - ion battery, comprising: A solid - state anode capable of intercalating and de - intercalating lithium ions; A solid - state cathode capable of intercalating and de - intercalating lithium ions; and A solid - state lithium - ion - conducting separator sandwiched between the anode and the cathode; Wherein at least one of the solid - state anode, the solid - state cathode and the solid - state separator comprises a component having the composition according to claim 15.

23. The solid - state lithium - ion battery of claim 22, wherein the solid - state lithium - ion - conducting separator comprises the composition, and wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

24. The solid - state lithium - ion battery of claim 22 or claim 23, wherein the solid - state lithium - ion - conducting separator further comprises at least one of the following: (i) a polymer different from the copolymer; and (ii) an additive selected from clay, metal oxide, metal nitride, and lithium - conducting ceramic.

25. The solid - state lithium - ion battery of any one of claims 22 - 24, wherein the solid - state lithium - ion - conducting separator comprises a lithium - conducting ceramic, and wherein the lithium - conducting ceramic is selected from lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphorus sulfur chloride (LSPSCl), lithium germanium phosphorus sulfide (LGPS), lithium - conducting halide, closo - borate, and nido - borate.

26. The solid - state lithium - ion battery of any one of claims 22 - 25, wherein the solid - state lithium - ion - conducting separator is in the form of a film with a thickness less than 30 microns, and wherein the ionic conductivity of the film is 0.05 mS / cm or higher.

27. The solid - state lithium - ion battery of claim 22, wherein the solid - state anode comprises the composition, and wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

28. The solid-state lithium-ion battery of claim 22, wherein the solid cathode comprises the composition, and wherein the lithium salt is selected from lithium bis(trifluoromethanesulfonyl)imide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

29. The solid-state lithium-ion battery of any one of claims 22-28, provided that the at least one additional monomer does not contain an epoxy group and is not formed from a compound containing an epoxy group.

30. A method for preparing the copolymer of any one of claims 1-12, comprising: dissolving a vinylene carbonate compound in a solvent; contacting at least one additional monomer with the vinylene carbonate compound and a polymerization initiator in the solvent under reaction conditions sufficient to copolymerize the vinylene carbonate compound with the at least one additional monomer, thereby obtaining the copolymer in a reaction mixture; precipitating the copolymer from the reaction mixture under conditions effective to precipitate the polymer; and separating the copolymer from the reaction mixture.

31. The method of claim 30, wherein the solvent is dimethyl sulfoxide, tetrahydrofuran, or N-methyl-2-pyrrolidone.

32. The method of claim 30 or claim 31, wherein the polymerization initiator is 2,2'-azobis(2,4-dimethylvaleronitrile).

33. The method of any one of claims 30-32, wherein the reaction conditions sufficient to copolymerize the vinylene carbonate compound with the at least one additional monomer include a temperature of 40°C to 100°C.

34. The method of any one of claims 30-33, wherein the method has a copolymer yield of greater than 50%.

35. A film comprising a polymer, the polymer comprising a first monomer of vinylene carbonate and a second monomer different from the first monomer and not having a glycidyl group; wherein the molar ratio of the first monomer to the at least one additional monomer is from 4:1 to 99:

1.

36. The film of claim 35, further comprising a metal salt, wherein the thickness of the film is less than 30 microns, and the ionic conductivity of the film is 0.05 mS / cm or higher.

37. A separator comprising the conductive film of claim 36.

38. A conductive layer in an electrode, comprising the conductive film of claim 36.

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