Polymer composition and method for producing the same

Abstract

A polymer formed from a first monomer consisting of vinylene carbonate and at least one second monomer that does not contain a glycidyl group different from the first monomer. Here, the molar ratio of the first monomer to the second monomer is 4:1 to 99:1. The polymer, preferably the copolymer, dissolves a metal salt, and the ionic conductivity of the composition of the copolymer and the metal salt can exceed 0.01 mS / cm. The polymer is applied to various components of solid-state batteries.

Description

Priority Claim

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 425,247, filed on 14 November 2022, which is incorporated herein by reference in its entirety. Field of Invention

[0002] This technology relates to novel polymers, particularly copolymers of vinylene carbonate compounds, fibers, and films produced therefrom. More specifically, this technology relates to novel polymers, more specifically copolymers, methods for producing the novel copolymers, and the use of the novel copolymers in battery separators, anodes, and / or cathodes. Background of the Invention

[0003] Metal-ion batteries, particularly lithium-ion batteries, are ubiquitous in modern electronic devices where improved performance is demanded, size constraints are increasing, and rechargeability is essential. The commercialization of lithium as a battery in the early 1990s revolutionized battery technology, providing disposable cells with significantly improved capacity and energy density, which are now widely used. Key to these advancements are the chemical and physical properties of lithium. Chemically, lithium is highly electropositive, readily donating valence electrons to achieve a stable structure. This makes lithium an excellent cathode component in batteries. During the charging phase of commercially available lithium-ion batteries, the graphite cathode is reduced, and lithium is added to replenish the internal charge. + It accepts ions. The positive electrode is oxidized, Li + Ions are released. During discharge, the graphite anode is oxidized and must release lithium ions. These lithium ions are accepted by the cathode and reduced. Due to its high reactivity and the lowest molecular weight among metallic elements, lithium is ideal for developing higher-power and lighter batteries. Now, more environmentally friendly rechargeable lithium-ion batteries have been developed and are suitable for modern high-frequency use applications that require frequent charging, such as portable electronic devices, military applications, and electric vehicles.

[0004] Conventional lithium-ion batteries utilize a liquid electrolyte solution to control the flow of lithium ions (i.e., electric current) between two electrodes known as the cathode (negative electrode) and anode (positive electrode), which can store ions. Between the anode and cathode is typically a microporous polymer layer, such as polyethylene or polypropylene, which serves to separate electrons and conduct ions between the two electrodes. During discharge, lithium ions move from the anode to the cathode through pores in the polymer layer, known as the separation zone, via the liquid electrolyte. This ionic current simultaneously drives an electron current, which flows through external circuits and powers connected devices. This process reverses during the charging cycle, with the ions flowing from the cathode to the anode. Most commonly, the cathode is constructed from an aluminum foil current collector coated with activated lithium cobalt oxide (LiCoO2, commonly called LCO).

[0005] Due to safety concerns regarding early lithium metal anodes, anodes coated with a graphite active material on a copper foil current collector have been used. This graphite active material has a lithium storage capacity that is only one-tenth that of a conventional anode, but it is very stable. This balance allows for batteries that can withstand repeated charge-discharge cycles, although the energy density is reduced (though this is acceptable). Unfortunately, if the battery structure is damaged by external force (such as a nail puncture) or if it is charged rapidly (where lithium metal is plated rather than lithium is inserted between the graphite sheets), rapid thermal runaway, explosion, or ignition can occur. In particular, lithium plating on graphite anodes is undesirable because the formation of metallic lithium dendrites can penetrate the porous separation and cause a short circuit inside the battery when it reaches the cathode. Also, when lithium plating adheres to graphite, the electrolyte can decompose, potentially leading to problems such as gas release, swelling, and shortened cycle life. This could pose a significant safety concern for lithium-ion batteries, particularly portable batteries transported on passenger aircraft and those used in the increasingly widespread electric vehicles. Much of the research on lithium-ion batteries has focused on improving these inherent safety hazards, specifically the non-uniformity of the lithium metal plating properties and the flammability of the liquid electrolyte solution.

[0006] While graphite anodes are safer than earlier lithium metal anodes, their energy capacity drops significantly to 372 mAh / g even in a fully lithium-ionized state (LiC6), which is about one-tenth of the 3600 mAh / g of solid lithium metal anodes. One promising area of ​​research is the development of solid anodes with alkali metal anodes. These anodes could offer more than three times the energy density of graphite anodes while maintaining uniform plating capabilities with charge cycle performance comparable to graphite anodes.

[0007] Another area of ​​research in lithium-ion batteries focuses on developing separators that can facilitate ion transport without requiring a liquid electrolyte solution. Conventional separators are microporous permeable membranes that separate electron diffusion from ion diffusion. A liquid electrolyte solution made of porous polyethylene or polypropylene (PE / PP) is required for ion transport. Many liquid lithium-ion batteries utilize lithium hexafluorophosphate dissolved in an organic carbonate solvent (e.g., ethylene carbonate and dimethyl carbonate) to facilitate ion transfer between the anode and cathode. The liquid electrolyte solution exhibits high conductivity at room temperature (e.g., bulk conductivity of 10 mS / cm). However, in conventional porous separator designs, the conductivity is reduced to 1 / 100th due to the bending of the pores. This separator plays a crucial role in battery safety. Due to the low melting points of polyolefin separators (PE is 135°C, PP is 165°C), they have poor thermal stability and can be damaged. When the temperature exceeds the melting point, this separation unit rapidly degrades, causing thermal contraction and contact between the positive and negative electrodes. This can result in a runaway thermal reaction, potentially leading to overpressure, casing rupture, and electrolyte ignition. These safety concerns could be significantly mitigated by developing a thermally stable solid separation unit capable of ion transport without requiring a flammable organic liquid electrolyte solution.

[0008] In recent years, efforts have been made to create batteries with solid polymer electrolytes that reduce or eliminate the need for liquid electrolytes. Conventional polymer electrolytes used for this purpose are polyethylene oxide (PEO), but the ionic conductivity of PEO at room temperature is orders of magnitude lower than that of conventional organic liquid electrolyte solutions. Other researchers have focused on mixtures of PEO and PEO-like polymers with other components to create solid electrolytes / membranes. For example, U.S. Patent No. 9,548,514 describes the use of poly(ethylene glycol) diacrylate (PEGDA) polymer, lithium bistrifluoromethanesulfonyliimide (LiTFSI) as a lithium salt, and succinonitrile (SCN) as a plasticizer, but these polymers have low molecular weight, tend to become waxy, and do not have sustainable mechanical integrity. U.S. Patent No. 9,287,540 describes the use of heat-resistant particles such as ceramics and other metal oxides in combination with conventional porous polymers such as crosslinked thermosetting polymer particles and modified thermoplastic polymers. U.S. Patent No. 8,574,772 describes forming a solid electrolyte using a Li-ion conductor containing a garnet-type compound and a phosphate group. While these types of solid polymers are said to minimize some of the safety issues associated with liquid electrolytes, they have drawbacks such as reduced mechanical properties, including decreased flexibility and high reactivity with ambient air and moisture.

[0009] Considering the above, there is a need for novel, flexible, lightweight, and ion-conductive polymers for use in improved solid-state batteries, while addressing the safety concerns associated with the predecessors of conventional liquid lithium-ion electrolytes. [Overview of the Initiative]

[0010] This technology relates to polymers and fibers and / or films produced from said polymers. More specifically, the polymers are copolymers comprising vinylene carbonate or vinylene derivatives, or analogs copolymerized with specific suitable monomers that can be designed for a wide range of applications as fibers and / or films. These polymers are available for various applications and are particularly useful for integration into various components of batteries when combined with conductive metal salts. For example, the polymers can be formed into films, which are preferably used as conductive separators or as solid electrolytes in and as part of the anode and / or cathode of a battery. Separators produced from the polymers of the present invention are useful as part of a battery. In some embodiments, the polymers can act as solid electrolytes or binders. Separators produced from the polymers of the present invention are useful in batteries, particularly metal-ion batteries. Examples of metal-ion batteries include, but are not limited to, lithium-ion, sodium-ion, potassium-ion, magnesium-ion, zinc-ion, aluminum-ion, or calcium-ion batteries. In one embodiment, the polymers of the present invention are formed into conductive films for use as single-layer or multi-layer separators. The present invention also relates to a method for synthesizing a polymer having physical and chemical properties suitable for use in a separation unit, as well as a battery using the separation unit.

[0011] Ideally, the polymers of this disclosure can dissolve metal ion salts without the use of liquid solvents and can be formed into conductive films and / or separators useful for separating the anode and cathode in a battery. In addition, or alternatively, the polymers can be used as part of the cathode and anode, mixed with conductive salts as a solid polymer electrolyte and / or as a binder for maintaining electrode integrity.

[0012] The batteries of this disclosure are useful for supplying power to a variety of electronic devices, such as mobile phones, smartwatches, tablets, laptops, automobiles, bicycles, drones, homes, and airplanes. Other applications include military applications such as battery-equipped backpacks, or other portable applications requiring power, such as drones, submarines, submersibles, tanks, and robots. Naturally, the polymers are not limited to battery applications and can be used in any application where polymer properties are beneficial, such as applications requiring a high melting point. Non-limiting examples of applications for the polymers and films manufactured therefrom include components in medical devices, aerospace, spacecraft, bearings, pumps, pistons, chromatography columns, and electrical cables.

[0013] In one embodiment, the disclosure relates to a copolymer comprising, as a copolymerization unit, a vinylene carbonate compound as a first monomer and at least one additional monomer different from the first monomer and copolymerizable with the first monomer, wherein the at least one additional monomer does not contain a glycidyl group. In some embodiments, the disclosure relates to the copolymer described herein, wherein 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 4:1 to 99:1.

[0014] In another embodiment, the present disclosure relates to a method for preparing the above copolymer. The method comprises dissolving the vinylene carbonate compound in a solvent; contacting the 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 to obtain a copolymer in a reaction mixture; precipitating the copolymer from the reaction mixture under conditions effective for precipitating the polymer; and isolating 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 the at least one additional monomer optionally include a temperature of 40°C to 100°C. Advantageously, the copolymer yield of the method is preferably over 50%, over 75%, or over 90%.

[0015] In various embodiments, the first monomer is optionally selected from the group consisting of vinylene carbonate, derivatives of vinylene carbonate, and analogs of vinylene carbonate. The at least one additional monomer is poly(ethylene glycol) methacrylate (PEGMA), 1,3-propensultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylethylene carbonate (VEC), dimethyl vinyl phosphonate (DMVP), maleic anhydride (MA), diethyl vinyl phosphonate (DEVP), diethyl allyl phosphonate (DEAP), or N-vinylpyrrolidone (NVP) (1-vinylpyrrolidine-2-one), N-methylmaleimide, vinylene sulfate, vinylene sulfite, vinylethylene sulfite, or butadiene sulfone. The following are optionally selected from the group consisting of vinyl sulfonic acid (VSA), N,N-dimethylvinyl sulfonamide, vinyl sulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphosphoran-2-oxide, metallic vinyl sulfonate, metallic vinyl phosphonate, metallic fluoro(vinyl)phosphinate, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metallic trifluoro(vinyl)boronate, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metallic 2-fluoro-2-vinyl-1,3,2-dioxaborolate-4,5-dione. In some optional embodiments, the at least one additional monomer comprises one or more of poly(ethylene glycol) methacrylate (PEGMA), vinylethylene carbonate (VEC), and / or dimethyl vinyl phosphonate (DMVP). In some arbitrary embodiments, 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 additional monomers that are distinct from each other and optionally selected from any of the aforementioned compounds.

[0016] In various embodiments, the copolymer may or may not be crosslinked. The molecular weight of the copolymer is arbitrarily 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, or greater than 250,000 Da. In terms of range, the molecular weight is preferably in the range of 250,000 Da to 2,000,000 Da, for example, 680,000 Da to 2,000,000 Da. The density is 0.5 g / cm³. 3 ~2.5 g / cm 3 This is within the range. Unless otherwise specified, "molecular weight" as used herein refers to the weight-average molecular weight (Mw). The copolymer may have a melting point of 200°C or higher, or it may not have a melting point, in which case it preferably has an oxidation point of 350°C or higher.

[0017] In another embodiment, the disclosure relates to a composition comprising the copolymer and a metal salt. The metal salt optionally comprises a metal ion selected from the group consisting of alkali metals, alkaline earth metals, aluminum, and zinc. The metal salt is preferably a lithium salt. For example, the lithium salt may be selected from the group consisting of 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 is preferably 0.01 mS / cm or higher when measured by electrochemical impedance spectroscopy at 25°C. The composition optionally contains Li O / Li + It exhibits a decomposition initiation current of 4.5 volts or more. The composition optionally has a lithium salt content of 20% to 80% by weight, based on the total weight of the composition. In another embodiment, the disclosure relates to a film, filament, nonwoven web, or fabric comprising the above composition.

[0018] In another embodiment, a solid-state battery is disclosed comprising a solid anode, a solid cathode, and a solid metal ion conductive separator sandwiched between the solid anode and the solid cathode, wherein at least one of the solid anode and the solid metal ion conductive separator contains a component having the above composition. In a related embodiment, the disclosure relates to a solid lithium-ion battery comprising a solid anode capable of inserting and removing lithium ions, a solid cathode capable of inserting and removing lithium ions, and a solid lithium ion conductive separator sandwiched between the anode and the cathode, wherein at least one of the solid anode, the solid cathode, and the solid separator contains a component having the above composition. The solid lithium-ion conductive separation unit optionally comprises the above composition, where the lithium salt is selected from the group consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi. The solid lithium-ion conductive separation unit optionally further comprises at least one of the additives selected from the group consisting of (i) a polymer different from the copolymer, and (ii) clay, metal oxides, metal nitrides, and lithium-conducting ceramics. In some embodiments, the solid lithium-ion conductive separator comprises a lithium-conductive ceramic, which is selected from the group consisting of lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphate sulfur chloride (LSPSCl), lithium germanium phosphate sulfide (LGPS), lithium-conductive halides, clothoborates, and nidoborates. Optionally, the solid lithium-ion conductive separator is in the form of a film with a thickness of less than 30 microns, wherein the ionic conductivity of the film is 0.05 mS / cm or higher.The solid anode optionally comprises the above composition, where the lithium salt is selected from the group consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0019] In another embodiment, the present disclosure relates to a film comprising a polymer containing a first monomer of vinylene carbonate and a second monomer different from the first monomer but without a glycidyl group, wherein the molar ratio of the first monomer to the at least one additional monomer is 4:1 to 99:1. The film optionally further contains a metal salt, has a thickness of less than 30 microns, and has an ionic conductivity of 0.05 mS / cm or more. The conductive film may be in the form of a separation portion or conductive layer in an electrode such as a battery. [Brief explanation of the drawing]

[0020] The nature and advantages of the technology described herein can be further understood by referring to the remainder of this specification and the drawings.

[0021] Figure 1 shows the polymer synthesis procedure according to the embodiments of this disclosure.

[0022] Figure 2 shows a perspective view of a cross-section of a lithium metal-based battery according to an embodiment of the present disclosure.

[0023] Figure 3 shows a perspective view of a cross-section of a solid isolation unit for a solid lithium metal battery according to an embodiment of the present disclosure.

[0024] Figure 4(a) shows a sterically inhibited polymerization reaction according to an embodiment of the present disclosure, and Figure 4(b) shows a copolymerization reaction according to an embodiment of the present disclosure.

[0025] Some of the above drawings are shown as schematic diagrams. It should be understood that these drawings are for illustrative purposes only and are not to scale unless specifically stated to be to scale. Furthermore, these drawings are provided as schematic diagrams to aid understanding and may not include all aspects or information compared to realistic representations, and may contain exaggerations for illustrative purposes. In the accompanying drawings, similar components and / or features may be given the same reference label. Furthermore, components of the same type may be distinguished by adding letters after the reference label to differentiate similar components. Where only the first reference label is used in this specification, the description is applicable to any similar component having the same first reference label, regardless of the letters. Detailed Description of the Invention

[0026] Introduction

[0027] Embodiments of the present invention relate to polymers, and fibers and / or films manufactured from said polymers. The fibers and / or films can function as separators, or as part of an anode and / or cathode. In particular, the polymer may be incorporated as part of a separator, as part of an anode (as an electrolyte), or as part of a cathode (as an electrolyte). The separators are useful in batteries, particularly metal-ion batteries. Examples of metal-ion batteries include, but are not limited to, lithium-ion, sodium-ion, potassium-ion, magnesium-ion, zinc-ion, aluminum-ion, or calcium-ion batteries. The disclosure also relates to methods for synthesizing said polymers having physical and chemical properties that are ideally suitable for use in separators and electrodes for batteries. Although primarily described in the context of energy storage systems, it will be understood that the polymers, fibers, and films described herein may also be used in other applications.

[0028] In one embodiment, the disclosure relates to a polymer formed from at least a first monomer comprising a substituted or unsubstituted vinylene carbonate or an analog or derivative thereof, and a second monomer different from the first monomer and without a glycidyl group, wherein the molar ratio of the first monomer to the second monomer is 4:1 to 99:1. In one embodiment, the disclosure relates to a copolymer comprising, as a copolymerization unit, a vinylene carbonate compound as the first monomer, and at least one additional compound different from the first monomer (e.g., an additional monomer or a second monomer) copolymerizable with the first monomer. However, the at least one additional compound does not contain a glycidyl group. Here, the molar ratio of the first monomer to the at least one second monomer is 4:1 to 99:1. In some embodiments, 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 disclosure relates to a method for synthesizing the copolymer, the method comprising: dissolving the vinylene carbonate compound in a solvent; contacting the at least one additional compound (second monomer) with the vinylene carbonate compound and a polymerization initiator in the solvent under reaction conditions sufficient to copolymerize the vinylene carbonate compound (first monomer) with the at least one additional compound (second monomer) to obtain a copolymer in a reaction mixture; precipitating the copolymer from the reaction mixture under conditions effective for precipitating the polymer; and isolating the copolymer from the reaction mixture.

[0029] In another embodiment, the Disclosure relates to a method for synthesizing the polymer, the method comprising: (i) supplying a first monomer having substituted or unsubstituted vinylene groups in a solvent; (ii) preferably adding a second monomer in the same solvent (wherein the second monomer is different from the first monomer and does not contain glycidyl groups); (iii) contacting the first monomer with the second monomer in the presence of the solvent and an initiator, and under reaction conditions sufficient to form a reaction mixture containing the polymer; and (iv) mixing a precipitant, such as water or methanol, with the reaction mixture under conditions effective for precipitating the polymer.

[0030] In these embodiments described above, the molar ratio of the first monomer to the second monomer used to form the polymer is preferably in the range of 4:1 to 99:1.

[0031] Polymers and methods for producing polymers

[0032] Referring to Figure 1, selected operations of polymer synthesis method 10 are shown. In operation 15, the first monomer may be supplied, preferably in one reaction solvent. In operation 20, the second monomer may be supplied, more preferably added to the first monomer. Alternatively, the second monomer may be supplied before the first monomer. In some embodiments, in operation 25, one third monomer (or optionally three or more monomers) may be supplied, or optionally added. Naturally, any order of addition may be adopted depending on the specific monomers selected. For example, any third monomer may be added before, after, or between the supply or addition of the first and second monomers. In operation 30, the monomers, including the first monomer, the second monomer, and the third monomer, if present, may be brought into contact with each other, preferably in the presence of a solvent and an initiator, and under reaction conditions sufficient to react and form a reaction mixture containing the polymer. In operation 35, method 10 may include recovering the polymer precipitate by contacting the monomers after a period of time necessary for synthesizing the polymer product, and then optionally adding a precipitant under conditions effective for precipitating the polymer product.

[0033] In this disclosure, the first monomer is a substituted or unsubstituted vinylene carbonate, or an analog or derivative thereof. In this context, the term “analog” refers to a compound that has a similar structure to another compound, e.g., vinylene carbonate, but is different with respect to a particular component. Importantly, the analog contains a ring having a carbonate bond and an intraring double bond. The term “derivative” refers to a compound formed from a parent compound, e.g., vinylene carbonate, through one or more chemical reactions, that has a similar structure to the parent compound, but is different with respect to one or more components, functional groups, atoms, etc.

[0034] Therefore, the first monomer may be an unsubstituted vinylene carbonate represented by the following formula (I). JPEG2026508794000002.jpg4367

[0035] In another embodiment, the first monomer is a substituted vinylene carbonate, or an analog or derivative of a vinylene carbonate. For example, the substituted vinylene carbonate may be represented by the following formula (II), where R1 and R2 are independently selected from any identical or different parts, as long as at least one of R1 and R2 is hydrogen. In some non-limiting embodiments, the substituted part on the vinylene carbonate may be selected from any substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, sultone group, sulfone group, maleate group, phosphonate group, sulfone group, or maleimide group. In some optional embodiments, in addition to the substituted or unsubstituted vinylene group, the first monomer may include an ether group such as an aldehyde, carboxylic acid, amide, or ester, or a carbonyl group. JPEG2026508794000003.jpg5575

[0036] Naturally, other substituted vinylene carbonate compounds, analogs, and derivatives are also possible, and even if such compounds are not included in general formula (II), they are still within the scope of this disclosure.

[0037] Polyvinylene carbonate homopolymers are typically obtained with low molecular weight and are often produced in low yields. Furthermore, such homopolymers exhibit low ionic conductivity in the presence of metal salts, which is thought to be due to the low mobility of the polyvinylene carbonate (PVCA) chain. The constituent elements of PVCA are five-membered carbonate rings, which cannot freely rotate around the bonds due to steric hindrance. As a result, as shown in Figure 4A (the carbonate portion is omitted for simplicity), the PVCA homopolymer chain is Li +It cannot coordinate well with small cations such as ions. Furthermore, vinylene carbonate homopolymers have low solubility in solvents and are modified by interactions with polar solvents. Due to the strong rotational hindrance of the homopolymer, such strong solvents can fragment the polymer chains during the solvation process. Therefore, vinylene carbonate homopolymers are difficult to dissolve in organic solvents, and it is necessary to process the homopolymer into fine particles before dissolution, often requiring heating and prolonged mixing to form a homogeneous solution. Moreover, since solutions of vinylene carbonate homopolymers are unstable, further processing is difficult. For these reasons, vinylene carbonate is usually polymerized in situ for battery applications, and removal of impurities or further modification is impossible.

[0038] While not bound by theory, it has been discovered that during polymerization, incorporating a second monomer copolymerizable with the first monomer (hereinafter also referred to as an additional compound or additional monomer) into the vinylene carbonate polymer chain within the disclosed monomer ratio reduces overall steric hindrance and improves the rotation and mobility of the polymer. As a result, surprisingly and unexpectedly, coordination with metal cations such as (but not limited to) lithium cations is improved, and polymer conductivity at low temperatures is enhanced. Thus, the second monomer can act as a “spacer” monomer in the copolymer. Some of the potential interactions enabled by this improved polymer flexibility are shown in Figure 4(b).

[0039] The second monomer, or at least one additional compound copolymerizable with the first monomer, may include any monomer different from the first monomer, as long as the second monomer does not contain a glycidyl group that could adversely affect the yield and performance of the entire copolymer. Beneficially, the polymers, and in particular the copolymers described herein, have improved stability in organic solvents such as DMSO, and therefore do not readily decompose in organic solvents, while preferably providing polymer weight-average molecular weights exceeding 50,000 Da, for example, exceeding 80,000 Da, exceeding 100,000 Da, exceeding 150,000 Da, exceeding 200,000 Da, or exceeding 250,000 Da, exceeding 500,000 Da, or exceeding 680,000 Da. It was discovered that by using one or more additional compounds as comonomers in combination with the first monomer, polymerization reactions that were impossible by other methods could be achieved with yields exceeding 50%, for example, exceeding 60%, exceeding 70%, exceeding 75%, exceeding 80%, exceeding 90%, or even close to 100%, and copolymers with higher molecular weights (Mw) than similar reactions could be formed. Furthermore, it was discovered that by using one or more such second monomers in combination with the first monomer, copolymers with desirable mechanical and electrochemical properties suitable for use in various battery components could be formed, as described above.

[0040] In one embodiment, the at least one additional compound copolymerizable with the vinylene carbonate compound (second monomer) does not contain linear α-olefins such as ethylene and propylene. Furthermore, the second monomer copolymerizable with the first monomer preferably does not contain ethylene carbonate or propylene carbonate. Moreover, the second monomer preferably does not contain diol acrylates such as butanediol and hexanediol, or glycol acrylates such as triacrylate, diacrylate and monoacrylate. However, any embodiment of linear α-olefin or any of the excluded monomers can be used as the third monomer.

[0041] In one embodiment, the disclosed polymers made from vinylene carbonate or its analogs or derivatives (collectively referred to as "vinylene carbonate compounds") and a second monomer do not require the use of nitrile compounds such as oxirane or succinonitrile (SCN). Therefore, the copolymer is preferably an uncrosslinked copolymer.

[0042] In an embodiment, the additional compound (second monomer) copolymerizable with the first monomer may contain a vinylene group characterized by the formula -CH=CH- that is substituted or unsubstituted. That is, the second monomer is any additional compound containing a vinylene group, i.e., R 3 -CH=CH-R 4 wherein R 3 and R 4 are each independently selected from any moiety that may be the same or different from each other. The second monomer may or may not contain at least one ring structure of 3, 4, 5, or 6 atoms. In this aspect, the moieties of R 3 and R 4 may be bonded to each other through one or more intervening atoms to form a ring structure. In some aspects, the intervening atoms may include an alkyl chain, an alkenyl chain, or a carbonate group (such as in the case of vinylene carbonate). In some aspects, the substituted or unsubstituted vinylene group includes a substituted or unsubstituted vinyl group.

[0043] In other embodiments, the second monomer may contain a substituted vinylene group of the formula -CR 5 =CR 6 -, wherein R 5 and R 6 are each independently selected from any moiety that may be the same or different from each other, but at least one of R 5 and R 6 is not hydrogen. That is, the second monomer may include any compound containing a substituted vinylene group, i.e., R 3 -CR 5 =CR 6 -R 4 wherein R 3 , R 4 , R 5 , and R6 These are selected independently from any parts that are identical or different from each other, but R 5 and R 6 At least one of them is not hydrogen. In particular, in some embodiments, R 3 , R 4 , R 5 , and R 6Two or more of the parts may be bonded to each other via one or more interfacing atoms to form a ring structure. In various arbitrary embodiments, the second monomer may be an unsaturated cyclic carbonate. In some specific embodiments, the second monomer (or at least one additional compound copolymerizable with the first monomer) may be 1,3-propensultone (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) (1-vinylpyrrolidine-2-one), N-methylmaleimide, vinylene sulfate, vinylene sulfite, vinylethylene sulfite, The second monomer may be butadiene sulfone, vinyl sulfonic acid (VSA), N,N-dimethylvinyl sulfonamide, vinyl sulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphosphoran-2-oxide, metallic vinyl sulfonate, metallic vinyl phosphonate, metallic fluoro(vinyl)phosphinate, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metallic trifluoro(vinyl)boronate, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, or metallic 2-fluoro-2-vinyl-1,3,2-dioxaborolate-4,5-dione. In the case of monomers containing a metal cation, the cation can 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), vinylethylene carbonate (VEC), or dimethyl vinyl phosphonate (DMVP). Other compounds that can be used as the second monomer include any of butyl cyanoacrylate, n-butyl acrylate, 2-acetoacetoxyethyl methacrylate, and pentafluoropropyl methacrylate.

[0044] The relative amounts and ratios of the first monomer and 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 may be in the range of 4:1 to 99:1, for example, 8:1 to 99:1, 15:1 to 999:1, 25:1 to 99:1, or 75:1 to 99:1. With respect to the upper limit, the molar ratio of the first monomer to the second monomer or at least one additional compound may 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 than these. Conversely, regarding the lower limit, the molar ratio of the first monomer to the second monomer or at least one additional compound may 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 much spacer monomer), for example 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 little spacer monomer), the resulting polymer may be too brittle. It has been found that by adopting the above ratios without being bound by theory, it is possible to obtain flexible, high-molecular-weight polymers with improved solubility in solvents and higher ionic conductivity compared to polymers formed from the first monomer alone.

[0045] The molar percentage of the first monomer in the polymer may be 80% or more, 82% or more, 84% or more, 86% or more, 88% or more, 90% or more, 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, or 98% or more, or higher, based on the total number of moles of all monomers used to form the monomer. In terms of range, the first monomer in the polymer may be provided in a molar percentage of 80% to 99%, 85% to 99%, or 90% to 99%.

[0046] The total molar percentage of the second monomer or at least one additional compound in the copolymer may be less than 20 mol%, for example, 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 than that. In terms of range, the second monomer may be present in amounts of 0.1 to 20 mol%, for example, 0.1 to 15 mol%, 0.1 to 12 mol%, 0.1 to 10 mol%, 0.1 to 8 mol%, or 0.1 to 6 mol%.

[0047] In one embodiment, at least one additional compound copolymerizable with the first monomer may include two additional compounds, namely a second monomer and a third monomer, the third compound or third monomer may be selected from either of the first or second monomers, as long as it is not the same monomer as the monomers selected for the first and second monomers. For example, any third monomer may be selected from PEGMA, VEC, and DMVP, as long as it is different from the second monomer used.

[0048] As described above, in operation 30, monomers comprising a first monomer, a second monomer, and an optional third monomer, if present, may be brought into contact with each other under conditions effective for reacting in a reactor to form a copolymer. The specific vessel and reaction conditions used can vary considerably. In some embodiments, the monomers are mixed in a reactor, which may be any suitable polymerization reactor capable of withstanding the specific temperature and pressure conditions used in the polymerization process. In one embodiment, the reactor is a vial, a round-bottom flask, a steel vessel, or a larger commercial polymerization reactor. The polymer may be synthesized in a continuous, semi-batch, or batch process. The polymer may be brought into contact at a temperature suitable for the polymerization process, which is usually determined by the initiator used. In some non-limiting embodiments, the temperature range may be 40–100°C, for example, 40–80°C or 50–70°C. The reaction may be carried out under atmospheric pressure or under high pressure, for example, 1–5 atmospheres. The reaction may be carried out over a period of several hours to several days, preferably 0.5 to 21 days, more preferably 0.5 to 14 days, and even more preferably 0.5 to 7 days or 0.5 to 2 days. The order in which the monomers are added can also vary considerably, depending largely on the reactivity of the selected monomers. Typically, all monomers are not added at once. Instead, in one embodiment, the least reactive monomer is added first, followed by the most reactive monomer. In one embodiment, the first monomer is added to the reactor before the second monomer. In another embodiment, the second monomer is added before the first monomer. In yet another embodiment, the first and second monomers are added to the reactor at least partially simultaneously. The monomers may also be added (added) in stages, if necessary.

[0049] In operation 30, the monomer may be brought into contact with a solvent and / or initiator. In a preferred embodiment, the solvent is selected based on its ability to dissolve the reagents (monomer and initiator) and the resulting polymer product. Furthermore, the solvent must be relatively inert and unreactive under the reaction conditions. The solvent must also be liquid at or near the reaction temperature and at room temperature. The solvent may be, but is not limited to, any solvent suitable for dissolving the monomer provided, such as dimethyl sulfoxide (DMSO), tetrahydrofuran, or N-methyl-2-pyrrolidone (NMP), or may include these.

[0050] In a preferred embodiment, the polymerization reaction is a free radical polymerization reaction. Therefore, an initiator may be provided to react with one or more monomers to initiate the reaction and form one or more intermediate compounds that can be sequentially bonded with one or more other monomers. In exemplary embodiments, the initiator may be azobisisobutyronitrile (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile), or may contain these. Other commercially available initiators that can be used include difunctional peroxides such as Trigonox® (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane), or VAZO TM Examples include diazo compounds such as 52. The amount of initiator used can vary considerably, but in some exemplary embodiments, it may be in the range of 0.01 to 1 mol%, for example, 0.01 to 0.8 mol%, 0.02 to 0.5 mol%, or 0.1 to 0.4 mol%.

[0051] In another embodiment, an organic solvent such as an alkane (e.g., hexane) may be used as a "non-solvent" medium to improve mixing without dissolving the monomer and initiator. In this way, the reaction can be carried out without the presence of a real solvent and without being carried out "neatly".

[0052] In operation 35, the specific steps used to recover the resulting precipitate, i.e., the synthesized polymer material, can vary considerably. In one embodiment, the step of recovering the product involves adding the reaction solution containing the product dropwise to a non-solvent, such as methanol, which sufficiently precipitates the high molecular weight product and solvates the ultra-low molecular weight components. Other non-solvents that can be used to precipitate the polymer include water and alkanes such as hexane, toluene, ethanol, isopropyl alcohol, and propanol. The solvent may be slowly added to form precipitated strands of polymer. The supernatant may then be decanted, the product washed with another non-solvent, such as MeOH, and then ground with the non-solvent, such as MeOH, for 1 to 48 hours, for example, 20 to 28 hours. The non-solvent may then be decanted, and the grinding may be repeated as needed. The isolated product may be dried, if necessary, under vacuum at a temperature of 20–60°C, e.g., 30–50°C, 35–45°C, or about 40°C for 0.5–4 days, e.g., 1–3 days, or about 2 days. A filamentous off-white polymer product is then obtained. In another embodiment, the polymer may be redissolved in a solvent and the process may be repeated.

[0053] The molecular weight of the polymer can vary mainly depending on its application. For example, in some applications, such as when used as an electrolyte in an electrode layer, a relatively low molecular weight, soft, or waxy polymer may be preferred. However, polymers intended for use as a separation unit are preferably higher in molecular weight and rigidity. Similarly, polymers with a medium molecular weight and a "sticky" consistency may be useful as binder compositions, such as electrode binder compositions. The precipitation step, particularly the non-solvent used in the precipitation step, can be important in determining the molecular weight of the polymer product. For example, selecting hexane as the non-solvent precipitant can result in the formation of an extremely high viscosity, high molecular weight polymer applied as a separation unit. Such polymers may require pulverization equipment, such as a rock crusher, to crush large, rock-like polymer products and form polymer powders useful for preparing slurries for battery separation units. The molecular weight of the polymer generally corresponds to the viscosity of the polymer in a 5-10 weight percent solution and can be qualitatively measured based on that viscosity. The preferred viscosity can vary depending on the desired application. For example, in the case of blade casting separation sections or spun fibers, polymers with a viscosity of 500 cP to 1000 cP, such as 500 to 750 cP or 750 to 1000 cP, may be desirable, but viscosities outside these ranges are also possible depending on the second monomer used.

[0054] Properties of polymers and films

[0055] The polymers of this disclosure are extremely useful in or as separation sections due to their unique structural and chemical properties. The separation section requires the use of a polymer film having a specific thickness, pore size, pore size distribution, porosity, and chemical stability. In addition to these properties, the separation section also possesses functional properties of electrical resistance (ER), permeability, and transport rate.

[0056] Depending on the application and manufacturing method of the polymer (e.g., precipitation method), the molecular weight of the polymer may be relatively low, moderate, or high. In some non-limiting embodiments, the weight-average molecular weight of the polymer may exceed 50,000 Da, for example, exceed 80,000 Da, exceed 100,000 Da, exceed 150,000 Da, exceed 200,000 Da, exceed 250,000 Da, exceed 250,000 Da, exceed 500,000 Da, exceed 680,000 Da, exceed 750,000 Da, exceed 1,000,000 Da, exceed 1,500,000 Da, or exceed 2,000,000 Da. In some embodiments, the molecular weight of the polymer may 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 range, the molecular weight may be in the range of 750,000 to 2,500,000 Da, for example, 900,000 to 1,300,000 Da, or 1,000,000 to 2,000,000 Da.

[0057] Similar to the molecular weight, the density of the polymer can also vary considerably depending on its application. For example, in some embodiments, the density of the polymer is 0.5 g / cm³. 3 For example, exceeding 0.6 g / cm³ 3 Exceeding 0.7 g / cm³ 3 Exceeding 1.0 g / cm³ 3 If it exceeds 1.5 g / cm³, or 1.5 g / cm³ 3 If it exceeds 2.5 g / cm³, and is 2.5 g / cm³ 3 It is less than . In terms of range, the density of the polymer is 0.5 to 2.5 g / cm³. 3 , 0.5~2.0 g / cm³ 3 , 0.5~1.5 g / cm 3 , 0.5~1.0 g / cm 3 , 0.6~0.9 g / cm 3 , or 0.7-0.8 g / cm³ 3 It could be within the range.

[0058] The polymer may or may not have a melting point, depending on the selected monomer. In most embodiments, the polymer does not have a melting point. This means that as the temperature of the polymer rises, it oxidizes (burns) in air before reaching its melting point. Therefore, in some embodiments, the polymer does not melt and has an oxidation point above 350°C, for example above 400°C, or above 450°C, optionally between 350°C and 450°C or between 375°C and 425°C. That is, with some second monomers, the polymer may have a melting point. In that case, the melting point is preferably above 200°C, above 300°C, or above 400°C.

[0059] The polymers of this disclosure have a dispersion degree 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 range, the dispersion degree may be in the range of about 1.5 to about 6, for example, about 2 to about 5, about 2.5 to about 4, about 3 to about 4, about 3.2 to about 4, or about 3.5 to about 4. The molecular weight of the polymers of this disclosure is arbitrarily 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, or greater than 250,000 Da. In one embodiment of the polymers of this disclosure, the polymer has a dispersion degree 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 a molecular weight greater than 50,000 Da (e.g., greater than 80,000 Da).

[0060] A key characteristic for many applications, particularly battery applications, is that the polymer should exhibit relatively high ionic conductivity when measured by electrochemical impedance spectroscopy (EIS). In particular, while the copolymer itself is not ionically conductive, it has the advantage of exhibiting high conductivity upon addition of a metal salt. Therefore, in one embodiment, this disclosure provides a composition containing the copolymer and metal salt described in the above embodiment.

[0061] In one embodiment, the metal salt comprises a metal ion selected from the group consisting of alkali metals, alkaline earth metals, aluminum, and zinc. In another embodiment, the metal salt is a lithium salt selected from the group consisting of 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.

[0062] Accordingly, the conductive films produced in accordance with this disclosure are preferably produced from the polymer, or more specifically from a composition containing the copolymer of this disclosure, as described above, and mixed with a metal salt to form a polymer blend composition, specifically a conductive polymer blend. The polymer blend can then be dissolved in a solvent and evaporated after blade casting to form the conductive film described herein. In various embodiments, the conductive film or separation portion of the present invention may be formed from the conductive polymer blend by any technique known for film production, such as blade casting, tape casting, blow molding, extrusion molding, spray molding, etc.

[0063] Numerous methods exist for producing films or separators from the polymers of this disclosure. Two main commercial methods are used: dry and wet. In the common dry method, the polymer is produced using an inflation film process in which a polymer molten material is extruded from an annular die and then flattened or flattened using nip rolls. In this method, a tubular film is filled with air and the film is cooled and solidified by continuously blowing in this air. It is also possible to produce films or separators from the polymers of the present invention using the cast film method. In the cast method, the extruded film is rotated on cooling rollers to rapidly cool the molten material. The film or separator may then be subjected to an annealing treatment to orient a crystalline film or separator structure. Furthermore, the film or separator may be subjected to either cold or hot stretching treatments.

[0064] The wet process may include several steps, including mixing, heating, extrusion, stretching, and removal of additives. In this method, the polymer is mixed with a solution and other additives (including metal salts if a separator is to be produced) to form a heated homogeneous solution. The resulting solution is extruded through a sheet die to produce a gel-like film, which is then stretched or oriented. The additives and volatile solvents used are then removed using heat in a drying process. In some embodiments, the polymers of the present disclosure may be formed into nonwoven fabrics or cloths. The nonwoven fabrics or cloths may be produced by continuously spinning filament fibers on a moving belt. The fibers are produced by extruding the polymer into a flowing polymer molten material. After this spinning process, the polymer appears as thin, continuous filaments. These filaments are then cooled, stretched, solidified, and converted into a mat. The mat can be used as a separator or constitute part of an anode or cathode. The mat can also be combined with ceramics for use as a separator. In a preferred embodiment, the polymer of the present disclosure is produced into fibers using electrospinning.

[0065] The ionic conductivity described herein is measured using an electrochemical impedance spectrometer on a conductive film formed from the polymer of this disclosure and LiTFSI in a mass ratio of 1:1.5. Here, the polymer is formed into a film before the conductivity is analyzed.

[0066] Optionally, the ionic conductivity (in mS / cm) of the conductive film of this disclosure at room temperature, when measured by an electrochemical impedance spectrometer, is greater than 0.01 mS / cm, 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 of the conductive film may be in the range of 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 conductivity values ​​are significantly better than those of conventional liquid electrolyte separations, which have relatively low conductivity at room temperature. Similarly, electrolytes of conventional PEO solid polymers containing LiTSFI salts may have a low conductivity of 0.001 mS / cm at room temperature.

[0067] In one embodiment, a film made from the polymer of the Disclosure, preferably when used as a separation section, has a thickness of less than 25 μm, less than 20 μm, less than 15 μm, less than 12 μm, less than 10 μm, or less than 7 μm. The thickness of the film of the present invention is typically in the range of 5 μm to 25 μm, for example, 5 μm to 15 μm, or 7 μm to 15 μm. Separation sections made from films made from the polymer of the Disclosure, more specifically from copolymer compositions, may also vary in thickness for use as part of a cathode or anode layer, as needed. The thickness of the film or separation section is measured according to ASTM D5947-96.

[0068] In another embodiment, the thickness of the conductive film of the present disclosure is in the range of 1 to 300 μm, for example, 10 to 250 μm, 50 to 250 μm, 50 to 200 μm, or 70 to 200 μm. If the film is intended to be used as a battery separator, a thinner thickness, for example, 5 to 25 μm, for example, 5 to 20 μm, 5 to 15 μm, or 5 to 10 μm may be preferred. In other embodiments, the thickness of the conductive film may exceed 10 μm, for example, exceed 50 μm, exceed 70 μm, exceed 100 μm, exceed 200 μm, or exceed 300 μm.

[0069] Porosity can be a very important property for obtaining high permeability, especially in films used as porous separators. Depending on the application, it may be preferable to have more uniform porosity so that the ionic current, i.e., Li ions, flows smoothly between the cathode and anode. The porosity of the film or separator of the present invention is measured using ASTM D-2873. The porosity of the film or separator of the present disclosure may be arbitrarily 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 separator is in the range of 30% to 70%, for example, 40% to 65%, 45% to 65%, or 50% to 65%.

[0070] In the manufacture of the films or separators of this disclosure, the films or separators are optionally stretched in the mechanical direction, the transverse direction, or both. When the film is used as a separator, shrinkage is preferably kept as small as possible. Thermal shrinkage is a common problem, especially with separators made from other plastic materials. The films and separators of the present invention exhibit little to no shrinkage even at temperatures above 150°C or higher. The shrinkage rate is calculated from the change in dimensions, i.e., shrinkage rate (%) = (L i -L f ) / L i It is ×100. Here, L i This is the initial dimension, L fThis is the final dimension after high-temperature exposure. In one embodiment, the film or separation of the disclosure manufactured by a wet process has a mechanical shrinkage rate of less than 15%, less than 10%, less than 7%, or less than 5% at 120°C. In one embodiment, the film or separation of the disclosure manufactured by a wet process has a transverse shrinkage rate of less than 10%, less than 7%, less than 5%, or less than 2% at 120°C.

[0071] The films or separators of this disclosure preferably have excellent tensile strength properties. Tensile strength can be measured in the mechanical direction and the transverse direction. Often, this depends on the manufacturing method. Uniaxially oriented films or separators have tensile strength measurements in one direction, while biaxially oriented films or separators have tensile strength measurements in both directions. Tensile strength can be measured according to ASTM D88-00. Ideally, the films or separators have sufficient mechanical strength to minimize neck formation or narrowing that occurs during winding or unwinding during battery assembly. In a preferred embodiment, the mechanical tensile strength of the films or separators of this disclosure is 1000 kg / cm². 2 , 1100 kg / cm² 2 , 1200 kg / cm 2 , or 1400 kg / cm² 2 In other embodiments, the lateral tensile strength of the film or separation portion of the present disclosure is 700 kg / cm². 2 750 kg / cm 2 , 800 kg / cm 2 , or 850 kg / cm² 2 It may exceed [a certain value]. Furthermore, when measured by cyclic voltammetry, the conductive film of this disclosure has a Li O / Li + A voltage exceeding 4 volts, preferably Li O / Li + For a voltage exceeding 4.5 volts, more preferably Li O / Li + For voltages exceeding 5 volts, the current is 0.1 mA / cm². 2 It is preferable to exhibit a current density of less than Li. In another embodiment, the conductive film of the present disclosure is LiO / Li + in the range of 3 to 5 volts with respect to, for example, Li O / Li + at a voltage in the range of 4 to 5 volts with respect to Li / Li or 4.5 to 5 volts with respect to LiO / Li⁺, having a normalized current of less than 0.1 mA / cm 2 In yet another embodiment, the conductive film of the present disclosure has a normalized current of less than 0.1 mA / cm at a voltage exceeding 4.2 volts with respect to Li O / Li + at a voltage exceeding 4.5 volts with respect to, for example, Li O [[ID=!15]] / Li + at a voltage exceeding 4.7 volts with respect to Li O / Li + at a voltage exceeding 4.8 volts with respect to Li O / Li + at a voltage exceeding 5 volts with respect to Li O / Li + having a normalized current of less than 0.2 mA / cm. In another embodiment, the conductive film has a normalized current of less than 0.2 mA / cm at a voltage in the range of 3 to 5 volts with respect to Li 2 for example, in the range of 4 to 5 volts with respect to Li O / Li + or in the range of 4.5 to 5 volts with respect to Li O / Li + at a voltage in the range of 4 to 5 volts with respect to Li O / Li + or in the range of 4.5 to 5 volts with respect to Li 2 having a normalized current of less than 0.2 mA / cm.

[0072] The point at which the current begins to flow without being hindered is regarded as the decomposition start current in the art. At this point, the polymer material constituting the film or the separator decomposes, adversely affecting the integrity of the film and the separator, as well as the usefulness in the battery. In one aspect of the present disclosure, the decomposition start current of the conductive film exceeds 4.5 volts with respect to Li O / Li + for example, exceeds 4.7 volts with respect to Li O / Li + exceeds 4.8 volts with respect to Li O / Li + exceeds 4.8 volts with respect to LiO / Li + exceeds 4.9 volts with respect to Li O / Li + or may exceed 5 volts with respect to Li, more preferably exceed about 6 volts, and most preferably exceed about 7 volts.

[0073] Conventional separators had the problem that the compositions constituting the separator decomposed chemically and physically under low voltages. For example, a conventional polyethylene oxide lithium solid polymer electrolyte (PEO) is considered to be stable only up to about 3.7 V with respect to Li O / Li + . A conventional porous separator injected with a liquid electrolyte is considered to be stable only up to about 4.25 V with respect to Li O / Li + . As a result, when charging exceeds the voltage at which the decomposition start current begins to flow, the electrolyte or the separator decomposes. In order to increase the energy density of the battery, it is desirable to charge to a higher voltage without decomposing the electrolyte and the separator.

[0074] The conductive film of the present disclosure is produced from a polymer blend composition containing the polymer of the present invention and a metal salt such as one or more lithium bis(trifluoromethanesulfonyl)imides (LiTFSI). The polymer blend composition and the conductive film produced therefrom are substantially more stable when the conductive film has a polymer composition start current generated at a high voltage. This effect is revealed by the measurement and interpretation of cyclic voltammetry (CV), a kind of electrochemical analysis technique for measuring current as a result of an applied voltage. As the voltage increases, the current is measured, and if the polymer blend composition of the conductive film is electrochemically stable, the change in current remains relatively small. This change continues until the decomposition start voltage is reached, and it is visually confirmed that the current increases without being hindered when the decomposition start voltage is reached. For example, in some examples of the present disclosure, surprisingly and unexpectedly, Li O / Li +A relatively constant current was observed up to approximately 5 volts.

[0075] The synthetic polymer can be molded into a wide variety of forms depending on the application. For example, in some embodiments, the polymer can be molded into fibers, such as fiber mesh, and / or films. To form the fibers and / or films, the synthetic polymer may be spun into fibers, as described above, for example by electrospinning or air-jet spinning. In applications involving separation units, it may be desirable to form the polymer film using the blade casting method, as described above.

[0076] When forming fibers and / or films, one or more additives may be introduced into the synthetic polymer. For example, the additives may be metal oxides, nitrides, borates, or lithium-conducting ceramics. Specific examples of such additives include silica, low-density lightweight lithium-conducting ceramics (e.g., Li1+xAlxTi2-xP3O12(LATP), LLZO), clays such as montmorillonite and attapulgite, zinc oxide, or boron nitride / vanadium.

[0077] Battery applications

[0078] As described above, the polymers of the Disclosure may be incorporated into various embodiments of solid-state batteries. Referring to Figures 2 and 3, embodiments of a solid separator 131 for a solid lithium-ion battery are shown, in addition to a high-energy-density lithium solid anode 111 for a solid-state battery 100. Referring to Figure 2, the solid-state battery 100 includes a solid anode 111 comprising a solid electrolyte 112 having a fibrous backbone, the solid electrolyte 112 optionally comprising the polymers of the Disclosure. The solid-state battery 100 may also include a metal ion deposit 120. The solid-state battery 100 also includes a cathode 113 having a solid cathode current collector 132. The solid separator 131 is positioned between the anode 111 and the cathode 113, and one or more of these may together or separately contain the polymers of the Disclosure.

[0079] The solid anode 111 may be formed from one or more layers of a solid electrolyte 112, which may be formed from a fibrous skeleton containing the polymer of the Disclosure. Generally, the solid anode 111 may be understood as a cathode or reducing electrode that emits electrons to an external circuit and oxidizes during discharge. The cathode 113 may be understood as a positive electrode or oxidizing electrode that receives electrons from an external circuit and is reduced during discharge. In this embodiment, the solid anode 111 may consist of a solid electrolyte 112 that can be understood as an interconnected fibrous skeleton. Ideally, the solid electrolyte contains a lithium salt dissolved as a solid solution in the dry polymer of the Disclosure. Naturally, the solid electrolyte must be conductive to suitable metal ions, typically lithium ions. The interconnected fibrous skeleton of the solid anode 111 containing components made from the polymer of the Disclosure may have a variety of properties and may be flexible or rigid. In the case of a ceramic fiber skeleton, the ceramic may be used to provide the structure or support for the solid anode 111 and the solid battery 100. Furthermore, ceramic fibers may be used in combination with or in conjunction with the polymers of this disclosure. Since the ceramic fibers provide conductivity to lithium ions but not to electrons, lithium metal cannot be deposited on the fibers. Instead, lithium metal is plated at the interface between the lithium-conductive ceramic fibers and the current collector. Thus, the plated lithium fills the voids between the conductive fibers. The lithium metal in the metal ion deposit 120 may provide the electronic conductivity of the solid-state battery 100. Meanwhile, the solid ceramic framework / skeleton may provide volume support, a surface layer for the metal ion deposit 120, and lithium ion conductivity.

[0080] One advantage of using the lithium-conductive ceramic fiber mat of this disclosure is the suppression of expansion and contraction caused by plating and delamination of lithium metal during cycling. With the fiber mat, plating and delamination occur favorably within the fiber mat framework, thereby preventing the expansion and contraction associated with many conventional solid-state batteries. In one embodiment, the polymer of this disclosure is mixed with or coated with ceramic to impart pores and / or flexibility. Thus, one means of manufacturing, "pre-lithifying," and / or operably engaging the metal ion deposit 120 with the fiber framework of the solid electrolyte 112 may be by partial melt injection of lithium metal into the treated ceramic framework. Initially, only a small amount of lithium metal needs to be injected into the pre-cell assembly of the solid anode 111. When only a small amount of lithium metal is injected into the pre-cell assembly of the solid anode 111, most or all of the reversible lithium that gives the cell capacity is supplied from the cathode 113 of the final assembly.

[0081] The lithium conductive portion of the solid anode 111 of the solid battery 100 may be a polymer framework within the solid electrolyte 112, which is composed of the polymers of the present disclosure. The polymer framework of the solid electrolyte 112 within the solid anode 111 may provide the additional advantage of flexibility. This can result in various advantages and balances at both the individual cell or layer level of the solid battery 100. Requirements for the polymer framework of the solid anode 111 and the material deposited therein optionally include (a) having a melting point above the melting point of lithium metal (about 180°C), (b) being nonconductive to lithium ions, and (c) impregnating the structure of the solid electrolyte 112 with a lithium-conducting material (e.g., other conductive polymers containing the corresponding lithium salt (e.g., lithium bis(trifluoromethanesulfonyl)imide / LiC2F6NO4S2 / LiTFSI), or ceramic particles embedded on the polymers of the present disclosure and / or on their surface). In such embodiments, additional components, manufacturing methods, and further variations may exist with various advantages and balances. These may include a fibrous mat that extends throughout the solid anode 111 and solid electrolyte 112. Furthermore, not all coatings for ceramic fiber frameworks are applicable to polymer or polymer fiber frameworks, and not all properties and features of ceramic fiber frameworks are directly applicable to polymer or polymer fiber frameworks, although some are.

[0082] Referring to Figure 3, a solid isolation section 131 for a battery such as a solid lithium-ion battery is shown. Schematically, the solid isolation section 131 for a solid lithium-ion battery may be formed in the form of one or more sheets. Each sheet has a microstructure. This structure may include, but is not limited to, a main polymer 320 of the present disclosure (illustrated as the thicker of two groups of long fibers throughout the solid isolation section 131), which may be formed from the first and second monomers described herein. The polymer of the present disclosure preferably has sufficient structural integrity to not require further support, but in some arbitrary embodiments, this structure may also include a structural polymer 330 (illustrated as the thinner of two groups of long fibers throughout the solid isolation section 131) and / or a reinforcing additive 310 (illustrated as a group of circles throughout the solid isolation section 131). Each surface of the solid separator 131 may have its own or different characteristics, qualities, chemical composition, etc., and / or combinations thereof, but for the purposes of this disclosure, it should be understood that the upper surface 340 and the lower surface 350 may be considered to have indistinguishable properties. That is, if the upper surface 340 operably engages with the cathode 113, the lower surface 350 will operably engage with the anode 311. Figure 3 is not a precise, or explicitly depicted, microscopic view or structure of the solid separator 131, but is an illustrative diagram to further illustrate the purpose, structure, and formation of the solid separator 131. Furthermore, those skilled in the art will understand the nature of the cross-sectional view in Figure 3 and will understand that it may represent only a small portion of the materials required even for a single-cell solid lithium-ion battery. The thickness of the solid separator 131 is understood to be generally uniform, although a thickness gradient may be apparent at a microscopic level. The solid separator 131 is understood to be very thin, have a large surface area, and low density. Other objective characteristics of the solid separation unit 131 will be understood and explained below.

[0083] As shown in Figure 3, any structural polymer 330 can be understood to be arranged overlappingly across the length, width, and depth of the solid separation section 131, and to be generally and / or uniformly distributed throughout the solid separation section 131. The properties of the solid separation section 131 are (i) lithium conductivity and (ii) electronic insulation. An additional property that is not essential but is considered beneficial is low material density, which may be necessary to obtain a high-energy-density cell. As mentioned above, the lowest-density solid material is polymer, so the lithium-conducting polymers of this disclosure are excellent candidates for the solid separation section 131, providing the backbone of the solid cell while simultaneously conferring high-energy-density properties. Lithium conductivity in the polymer is conferred by Li+ coordination sites with high mobility. Such sites may include silicon-based polymers with similar functional groups such as ether oxygen, carbonate, or siloxane. Other Li+ conductive sites on the polymer include nitrogen, phosphorus, or sulfur systems, as found in polydopamine, polyimide, polyphosphazene, or polysulfonates. Preferably, the overall thickness of the solid separation section 131 should be less than 30 microns, for example, 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 than or less than 10 microns. The solid separation section 131 needs to be self-stable even in humid air. These requirements, in addition to benefiting the overall utility and functionality of the solid separation section 131, may facilitate the adoption of the solid separation section 131 and general solid batteries by battery manufacturers in various markets. These strength coefficients can be improved by mixing with inorganic materials such as reinforcing additives 310 to create composite materials. In addition to the main polymer 320 and structural polymer 330, these inorganic materials constituting the reinforcing additive 310 also preferably possess lithium conductivity and have low density.Inorganic additives that may constitute the reinforcing additive 310 include clay, metal oxides, nitrides, or lithium-conducting ceramics (e.g., lithium titanium aluminum phosphate (LATP), lithium zirconium lanthanum oxide (LLZO), lithium silicon phosphorus sulfur chloride (LSPSCl), lithium germanium phosphate (LGPS), lithium-conducting halides, closoborates / nidoborates, etc.), and / or combinations thereof. Electronically insulating carbon-based additives may also be used to form the reinforcing additive 310. Whether inorganic or carbon-based, the reinforcing additive 310 may remain in the composite material in small amounts as long as it remains useful for reinforcing the composite material. The exemplary amount of the reinforcing additive 310 may be less than 10% by weight or about 10% by weight.

[0084] The main polymer 320, the optional structural polymer 330, and the optional reinforcing additive 310, or any combination of any two of these, can be important in influencing the overall utility, structure, function, and application of the solid separation unit 131. An exemplary method of combining the main polymer 320, the structural polymer 330, and / or 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. Furthermore, the production of the solid separation unit 131 by electrospinning can be understood as producing a highly porous mat (i.e., a fibrous mat with porosity greater than 90%), and then injecting a conductive polymer. Those skilled in the art of nonwoven fabric manufacturing will understand that laboratory-scale electrospinning can generally be performed by applying a high voltage between a metal injection needle and a conductive plate. Electrospinning can be considered a more adaptable fiber spinning technique than conventional melt spinning. Electrospinning can be performed at room temperature and can produce randomly arranged or aligned fiber mats, depending on the desired mat structure. The fiber mat produced by this method can be left unreactive at room temperature and exposed to the atmosphere. Using needle electrospinning, it is also possible to obtain hollow core fibers by using a coaxial needle. This method can further reduce the weight of the solid separation unit 131. Although there are challenges in scaling up this well-known laboratory procedure, by modifying the viscous material, it is possible to spin fibers under voltage application via a conductive spiral rotating on the same principle, without using a needle. A scalable process can be realized by using a modified viscoloid that spins fibers while applying voltage by rotating a conductive spiral without using a needle. The use of this modified viscoloid technology may be important in the scalable production of the main polymer 320, structural polymer 330, and reinforcing additive 310, or a combination of two of these, to form the solid separation unit 131 in a solid porous mat.

[0085] Methods of forming the solid separator 131 by blade casting may also include forming the solid separator 131 by blade casting of the main polymer 320, the structural polymer 330, and the reinforcing additive 310, or any combination of any two of these. Those skilled in the art may form a robust, porous fibrous mat suitable as a solid separator 131 having the lightweight properties described herein by blade casting of a mixture of polymers, inorganics, and / or lithium salts. Blade casting may have the further advantage of being an already scalable process and a conventional process already known in the battery industry. For example, substantially all battery electrodes are assembled by this technique. The method of blade casting this mixture may offer more advantages in a solid separator 131 containing a polymer blend to achieve the desired strength at the required thickness. However, if the main component of the solid separator 131 is a polymer composition and the polymer composition is self-supporting, it may be difficult to obtain a thin (e.g., less than 30 microns or about 30 microns) large-area solid separator 131. This method is more suitable for a complete stacked cell assembly process in a complete in-house multi-cell battery assembly process from top to bottom, where the solid isolation unit 131 is stacked on the electrodes. In this case, the assembly process can be carried out simultaneously with the manufacture of the solid isolation unit 131, thus eliminating the requirement for self-supporting operation mentioned above. Materials that can be used as components of the blade cast slurry for manufacturing the solid isolation unit 131 include, but are not limited to, fumed silica (inorganic additive) + G4 (tetraglyme, solvent) and / or LiTFSA (lithium salt), LiBOB, LiTFSI, LiBF2(C2O4), LiBF2(C2O4), C2O4Li2, CF3CO2Li, C6H5COOLi, other lithium salts, and / or combinations thereof.

[0086] In addition to combining the main polymer 320, structural polymer 330, and reinforcing additive 310, or any two of these, by electrospinning or blade casting to form the solid isolation portion 131, it may be even more important to provide an interface coating (or interfacing coating) at the interface with the anode or cathode. Since it may be desirable to maximize lithium conductivity throughout the entire thin (e.g., less than 30 microns or about 30 microns) solid isolation portion 131, additional treatment may be required on the upper surface 340 and / or lower surface 350 of the solid isolation portion 131 to allow the anode and cathode to be in such close proximity even in the presence of the solid isolation portion 131. In other words, the interface between the anode and / or cathode and the solid isolation portion 131 may require additional treatment to ensure the long-term operation, durability, and sustainability of the solid-state battery 100. This can be a particularly serious problem at the interface with the exposed lithium metal of the solid anode 111. The interface coating can generally be applied, formed, or otherwise present on the upper surface 340 and / or the lower surface 350. Examples of coatings that can stabilize and enhance this interface include, but are not limited to, graphite / graphene (i.e., carbon), nitride / borate (e.g., boron nitride, MgB2, Cu3N), metal alloys (e.g., Al coating from AlX3 or Al(NO3)3 salts dissolved in solution, In(TFSI)3, InF3, In(NO3)3, or In coating from salts of these dissolved in solution), sulfur (e.g., Li2S+S, LPS), or fluoroethylene carbonate (FEC) (i.e., fluoroethylene carbonate, cathode stabilizer additive).

[0087] Components manufactured or constructed according to this embodiment may feature improved electrical characteristics. For example, the battery may have a capacity of more than or about 1200 mAh / g, for example, more than or about 1225 mAh / g, more than or about 1250 mAh / g, more than or about 1275 mAh / g, more than or about 1300 mAh / g, more than or about 1325 mAh / g, more than or about 1350 mAh / g, more than or about 1375 mAh / g, more than or about 1400 mAh / g, or even greater. The aforementioned battery is characterized by having an energy density of over 500 Wh / kg or approximately 500 Wh / kg, for example, over 525 Wh / kg or approximately 525 Wh / kg, over 550 Wh / kg or approximately 550 Wh / kg, over 575 Wh / kg or approximately 575 Wh / kg, over 600 Wh / kg or approximately 600 Wh / kg, over 625 Wh / kg or approximately 625 Wh / kg, over 650 Wh / kg or approximately 650 Wh / kg, or higher.

[0088] Furthermore, in one embodiment, the separation portion made from a conductive film made from the polymer of the present disclosure is characterized by having an ionic conductivity of more than 0.01 mS / cm with respect to the disclosed polymer, as described above, and can also have an ionic conductivity of more than 0.05 mS / cm, more than 0.10 mS / cm, more than 0.15 mS / cm, or more than 0.20 mS / cm. In terms of range, the separation portion may have an ionic conductivity of any of 0.01 to 0.3 mS / cm, for example, 0.05 to 0.25 mS / cm, or 0.1 to 0.25 mS / cm.

[0089] Accordingly, in one embodiment, the present disclosure provides a solid-state battery comprising a solid anode, a solid cathode, and a solid metal ion conductive separator sandwiched between the anode and the cathode, wherein at least one of the solid anode and the solid separator comprises a component having a copolymer composition containing the aforementioned metal salt.

[0090] In one embodiment, the present disclosure provides a solid lithium battery comprising a solid anode capable of inserting and removing lithium ions, a solid cathode capable of inserting and removing lithium ions, and a solid lithium ion conductive separator sandwiched between the anode and the cathode, wherein at least one of the solid anode, solid cathode and solid separator comprises a component having a copolymer composition containing the above-mentioned lithium salt.

[0091] In one embodiment of a solid lithium battery, the solid lithium ion conductive separator comprises the composition, wherein the lithium salt comprises one or more selected from the group consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi. The solid lithium ion conductive separator may further comprise (i) a polymer different from the copolymer, and / or (ii) at least one additive selected from the group consisting of clay, metal oxides, metal nitrides, and lithium-conductive ceramics. The solid lithium-ion conductive separation unit may include a lithium-conducting ceramic selected from the group consisting of lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphate sulfur chloride (LSPSCl), lithium germanium phosphate sulfide (LGPS), lithium conductive halide, clothoborate, and nidoborate. The solid lithium-ion conductive separation unit may be in the form of a film with a thickness of less than 30 microns, wherein the ionic conductivity of the film is 0.05 mS / cm or higher.

[0092] In another embodiment of the solid lithium-ion battery, the solid anode comprises the composition, the lithium salt being selected from the group consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0093] In another embodiment of the solid lithium-ion battery, the solid cathode comprises the composition, the lithium salt being selected from the group consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0094] With regard to the above description, it should be understood that the optimal dimensional relationships include variations in size, material, shape, form, position, function, method of operation, assembly, type of anode / cathode / battery container, type of connection, and application, all of which are intended to be encompassed in this disclosure. In this specification, the solid isolation unit 131 and the various parts and components described herein may include, but are not limited to, the solid anode 111, solid electrolyte 112, metal ion deposit 120, cathode 312, cathode current collector 132, etc., and / or combinations thereof, and are intended to include various overall sizes and corresponding sizes of various parts. In fact, these various parts and components of the solid battery 100 may vary in size, shape, etc., during the standard operation of the solid battery 100. The description of the solid isolation unit 131 herein mentions the advantages of electric vehicles and other electronic devices, but the present invention is not limited thereto. The solid isolation unit 131 for solid lithium-ion batteries of this disclosure, and batteries manufactured therefrom, can be applied to power other vehicles, computers, businesses, homes, industrial facilities, consumer and portable electronic devices, hospitals, factories, warehouses, government facilities, data centers, emergency backup, aerospace, space travel, robotics, drones, etc., and / or combinations thereof. The chemical formulas, metals, atomic and molecular compositions provided herein ("Disclosed Formulas") are for illustrative purposes only. Those skilled in the art will understand that variations of the disclosed formulas may provide a balance with the disclosed solid isolation unit 131 for solid lithium-ion batteries and may be substituted to achieve similar advantages to the solid isolation unit 131 for solid lithium-ion batteries of this disclosure. Furthermore, it is anticipated that various considerations may be taken into account with respect to the manufacture of batteries due to variations in materials and manufacturing techniques, including but not limited to polymers, alloys, metals, assemblies, tabs, welding, atmosphere composition, etc., and combinations thereof.However, while methods for manufacturing and assembling batteries are envisioned to achieve results such as improved energy density per unit mass, higher operating current, increased battery durability and lifespan, a wider reliable operating range, safer batteries, and more efficient manufacturing methods, this disclosure is not limited to specific components, the advantages described and explained herein, and / or manufacturing methods described herein.

[0095] The present invention will be further understood by referring to the following non-limiting examples. Comparative examples are indicated as "CE" in the table below, where M3 is GLA or GMA. Example CE69 corresponds to Example 1 of CN110518282B. This example was observed to have a very low yield (14 wt%) and low viscosity, reflecting the low molecular weight. [Examples]

[0096] The following tables show various examples of the polymers formed that can be used in the separation section, such as the main polymer 320 of the solid separation section 131. Table 1 lists the examples and indicates the first monomer (M1), the second monomer (M2), and, if included, the third monomer (M3). These polymers were prepared according to the four synthesis protocols described below, namely Process A, Process B, Process C, and Process D. All examples labeled "CE" in Tables 1 and 2 are comparative examples. Table 1 JPEG2026508794000004.jpg19284JPEG2026508794000005.jpg192122JPEG2026508794000006.jpg191121JPEG2026508794000007.jpg19279

[0097] *Unless otherwise specified, all processes were performed at 60°C. ND = Not measured.

[0098] Legend for monomer abbreviations:Vinylene carbonate (VC), 4-vinyl-1,3-dioxolan-2-one (vinylethylene carbonate 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 vinyl phosphonate (DMVP), butyl cyanoacrylate (BCA), N-butyl acrylate (NBA), pentafluoropropyl methacrylate (PFMA), glycidal acrylate (GLA), glycidal methacrylate (GMA), N-methyl maleimide (NMM), and dimethyl vinyl phosphonate (DMVP). VAZO 52 refers to 2,2'-azobis (2,4-dimethylvaleronitrile).

[0099] Process A

[0100] A stirring bar was attached to a 25 ml reaction vial, and the first monomer (M1), second monomer (M2), and, if indicated, third monomer (M3), solvent, and initiator were charged under an argon atmosphere. Argon was sprayed over this mixture, and then the vial was sealed. The reaction vial was left in a heating block at the temperature shown in Table 1. Initiation was confirmed by the formation of bubbles. The vial was then stirred at the indicated temperature for the time shown in Table 1. An off-white viscous solution was produced, which was poured into approximately 250 ml of MeOH while stirring to form long polymer threads. The supernatant was decanted, the product was washed with MeOH, and then pulverized with MeOH for 24 hours. Decanting with MeOH and pulverization were repeated. Next, the isolated product was dried at 40°C for 2 days under vacuum (1 Torre) to obtain off-white polymer threads.

[0101] Process B

[0102] An overhead stirrer with nitrogen inlet / outlet was fitted to a 500 ml reaction vessel and purged with nitrogen. Under a nitrogen atmosphere, the flask was charged with the first monomer (M1), the second monomer (M2), the third monomer (M3) if specified, the solvent (99.9% anhydrous, 80 ml), and the initiator to obtain a clear solution. The flask was covered with aluminum foil to protect it from light and then heated in an oil bath to the temperature shown in Table 1. After the time shown in Table 1 had elapsed, the reaction mixture was removed from the heat to obtain a very viscous solution. A stirrer bar, nitrogen inlet, and dropping funnel were fitted to a 5 L reaction vessel and 2.5 L of MeOH was charged. Next, this viscous polymer solution was slowly added to the MeOH being stirred through the dropping funnel. A white precipitate was formed. The supernatant was decanted and the product was ground with MeOH for 24 hours. The MeOH was decanted and this process was repeated. The product isolated under vacuum (1 Torre) was dried at 40°C for 2 days to obtain filamentous, off-white polymeric products.

[0103] Process C

[0104] A 500 mL reaction flask was fitted with a stirring bar, gas inlet / outlet, and oil bath. The flask was purged with argon, and VC, hexane, and initiator were charged and heated to the temperature shown in Table 1. The first monomer (M1), second monomer (M2), and third monomer (M3) if indicated were weighed and mixed in vials for intermittent feeding. After 30 minutes, 6 ml of the monomer solution was added and the mixture was stirred for 16 hours at the temperature shown in Table 1. After 16 hours, a gel had formed beneath the hexane layer. A further 10 ml of the monomer mixture was added and the reaction was continued for another 24 hours. Next, the remaining monomer mixture was added and the reaction was continued and monitored by NMR. After 4 days, a small amount of unreacted M1 remained. Additional initiator was added and the reaction was continued overnight to obtain a translucent solid. The reaction mixture was cooled to room temperature, the hexane layer was decanted, the solid was pulverized, and washed multiple times with hexane. This solid was transferred to a 1-liter round-bottom flask, dried at 60°C using a rotary evaporator, and then dried in a vacuum oven at 60°C for 2 days.

[0105] Process D

[0106] A stirring bar was attached to a 20 ml reaction vial, and the first monomer, second monomer, solvent, and initiator were charged under argon. Argon was sprayed over the mixture, and then the vial was sealed. The reaction vial was left in a heating block at the temperature shown in Table 1. The progress of the reaction was monitored by NMR until the first monomer was consumed or the reaction stopped. When the reaction was complete, an off-white viscous solution was obtained. This was poured into 250 ml of stirred MeOH to form long polymer threads. The supernatant was decanted, the product was washed with MeOH, and then pulverized with MeOH for 24 hours. Decanting with MeOH and pulverization were repeated. Next, the isolated product was dried at 40°C for 2 days under vacuum (1 Torre) to obtain off-white polymer threads.

[0107] Surprisingly, Table 1 above shows that the monomers used in this disclosure yield much higher polymerization yields than the comparative examples. This generally corresponds to better monomer incorporation and more homogeneous polymers. While not bound by theory, polymers produced in the comparative examples, which have monomers containing glycidyl groups with ether links, are thought to dissociate in the presence of a solvent, resulting in undesirable low molecular weight polymers. This effect makes it more difficult to produce films useful in the present invention and has potentially detrimental effects in battery applications, particularly high-voltage battery applications.

[0108] Molecular weight determination by gel permeation chromatography (GPC), also known as size exclusion chromatography (SEC), was performed using an Agilent 1100 HPLC equipped with a thermostat-controlled column oven, refractive index detector, and tunable wavelength UV-Vis detector.

[0109] The columns used for separation were Agilent PLgel Mixed-C columns (5 μm, 300 mm × 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 approximately 5 μm gel particles made of a highly crosslinked 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.

[0110] A portion of the sample was transferred using a spatula to a glass vial fitted with a PTFE-lined metal screw cap. Next, the sample was 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.

[0111] The molecular weight (Mw) and dispersion of the polymers in Examples 23, 31, 50, and 53 were measured. Their molecular weights (Mw) were 50, 100 Da, 4,940 Da, 112,461 Da, and 81,500 Da, respectively. Their dispersions were 3.3, 1.6, and 3.9, respectively. 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, respectively. Surprisingly, the polymers of the present invention did not decrease in molecular weight after contact with a solvent (DMSO in this case). The molecular weight and dispersion of the samples were measured using data collected by refractive index (RI) detection. The data were analyzed using Agilent GPC / SEC software (Ver. 2.2). Calibration curves were prepared using narrow polyethylene oxide / glycol standard samples with molar masses ranging from approximately 200 to 1,500,000 g / mol. The two standard samples with the highest molar masses and the one with the lowest molar mass were not used because they were outside the column's exclusion and permeation limits. However, this calibration curve showed linearity up to the permeation limit (system peak, elution time approximately 16.7 minutes) (r² = 0.9947).

[0112] JPEG2026508794000008.jpg69166

[0113] Film formation

[0114] The obtained polymer was dissolved in a solvent and blade-cast. The parameters used for film formation are shown in Table 2 below. The thickness of the obtained polymer was also measured as described below and is listed in Table 2. Each of the polymers shown in the table above was dissolved in DMSO or NMP at a concentration of 15% by mass. Using this method, 1 gram of polymer can be dissolved in approximately 6 grams of DMSO. A metal salt, specifically lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), was added to the solution in the ratio shown in Table 2. Next, the obtained mixed solution was cast onto aluminum foil with a wet gap of 82-100 μm. This 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. For further testing, such as conductivity and thickness testing, the final film was laid to 1.327 cm². 2 The stamp was applied to a coin cell with a certain area. It was also observed whether the film was self-supporting.

[0115] conductive

[0116] The conductivity of the selected examples was measured based on electrochemical impedance spectroscopy (EIS) as described below and is shown in Table 2. When the conductive film had an initiation current of the polymer composition generated at high voltage, the polymer blend composition and the resulting conductive film were substantially more stable. This effect was revealed by measurement and interpretation using cyclic voltammetry (CV), a type of electrochemical potential measurement that measures current as a result of applied voltage. As the voltage was increased, the current was measured. Surprisingly and unexpectedly, high stability at high voltages was observed until the current increased significantly, as reflected in a stable normalized current at high potentials. In some examples (e.g., Example 50), stability was observed even at a high voltage of 5.0 V for Li+ / Li.

[0117] The methods, systems, apparatus, graphs, and tables described herein are for illustrative purposes only. Various procedures or components may be omitted, replaced, or added as needed in various configurations. For example, in alternative configurations, the Method may be performed in a different order than described, and / or various steps may be added, omitted, and / or combined. Also, features described for a particular configuration may be combined in various other configurations. Different aspects and elements of configurations may also be combined. Furthermore, technology is evolving, and many elements are for illustrative purposes only and do not limit this disclosure or claims. Also, the technology described herein may yield different results depending on the classification of different types of context recognition. Table 2 JPEG2026508794000009.jpg192116JPEG2026508794000010.jpg192114**These examples showed high conductivity due to the very low molecular weight of the resulting polymer. The film appeared to be plasticized with very short chains, like a wax-like pseudosolid. The film could not be lifted as a self-supporting membrane (the ease of lifting the membrane correlates with a significant increase in molecular weight). As mentioned above, polymers with higher molecular weights are desirable. This reduces the amount of polymer required, resulting in an increase in total salt content and improved "true" dry conductivity.

[0118] Embodiment

[0119] Embodiment 1 A copolymer comprising, as a copolymerization unit, a vinylene carbonate compound as a first monomer and at least one additional monomer that is different from the first monomer but copolymerizable with the first monomer, wherein the at least one additional monomer is a copolymer that does not contain a glycidyl group, and the molar ratio of the first monomer to the at least one additional monomer is 4:1 to 99:1.

[0120] Embodiment 2 The copolymer of Embodiment 1, wherein the first monomer is vinylene carbonate.

[0121] Embodiment 3 The copolymer of Embodiment 1, wherein the first monomer is a derivative or analog of vinylene carbonate.

[0122] Embodiment 4 The at least one additional monomer is poly(ethylene glycol) methacrylate (PEGMA), 1,3-propensultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylethylene carbonate (VEC), dimethyl vinyl phosphonate (DMVP), maleic anhydride (MA), diethyl vinyl phosphonate (DEVP), diethyl allyl phosphonate (DEAP), or N-vinylpyrrolidone (NVP), N-methylmaleimide, vinylene sulfate, vinylene sulfite, vinylethylene sulfite, or butadiene sulfone, vinyl sulfonic acid (VSA). A copolymer of any of the embodiments, selected from the group consisting of N,N-dimethylvinylsulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphosphoran-2-oxide, metallic vinyl sulfonate, metallic vinyl phosphonate, metallic fluoro(vinyl)phosphinate, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metallic trifluoro(vinyl)boronate, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metallic 2-fluoro-2-vinyl-1,3,2-dioxaborolate-4,5-dione.

[0123] Embodiment 5 The at least one additional monomer may be poly(ethylene glycol) methacrylate (PEGMA), 1,3-propensultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylethylene carbonate (VEC), dimethyl vinyl phosphonate (DMVP), maleic anhydride (MA), diethyl vinyl phosphonate (DEVP), diethyl allyl phosphonate (DEAP), or N-vinylpyrrolidone (NVP), N-methylmaleimide, vinylene sulfate, vinylene sulfite, vinylethylene sulfite, or butadiene sulfone, vinyl sulfonic acid (VSA), or N,N-dimethyl vinyl A copolymer of any of Embodiments 1 to 4, comprising two distinct additional monomers selected from the group consisting of sulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphosphoran-2-oxide, metallic vinyl sulfonate, metallic vinyl phosphonate, metallic fluoro(vinyl)phosphinate, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metallic trifluoro(vinyl)boronate, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metallic 2-fluoro-2-vinyl-1,3,2-dioxaborolate-4,5-dione.

[0124] Embodiment 6 A copolymer of any of Embodiments 1 to 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.

[0125] Embodiment 7 The copolymer is any of the embodiments described above, wherein the copolymer is not crosslinked.

[0126] Embodiment 8 The copolymer has a molecular weight exceeding 50,000 Da and a concentration of 0.5 g / cm³. 3 ~2.5 g / cm 3A copolymer of any of the embodiments having the density of .

[0127] Embodiment 9 The copolymer according to any of the embodiments, wherein the copolymer has a melting point of 200°C or higher.

[0128] Embodiment 10 The copolymer according to any of Embodiments 1 to 8, wherein the copolymer does not exhibit a melting point and has an oxidation point of 350°C or higher.

[0129] Embodiment 11 The copolymer according to any of the embodiments, wherein the copolymer has a molecular weight exceeding 80,000 Da.

[0130] Embodiment 12 A copolymer of any of the embodiments, wherein the at least one additional monomer does not contain an epoxy group and is not formed from a compound containing an epoxy group.

[0131] Embodiment 13 A composition comprising a copolymer according to any of the above embodiments and a metal salt.

[0132] Embodiment 14 The composition of Embodiment 13, wherein the metal salt comprises a metal ion selected from the group consisting of alkali metals, alkaline earth metals, aluminum, and zinc.

[0133] Embodiment 15 The composition of Embodiment 13, wherein the metal salt is a lithium salt.

[0134] Embodiment 16 The composition of Embodiment 15, wherein the lithium salt is selected from the group consisting of lithium bis(trifluoromethanesulfonylamide) (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0135] Embodiment 17 A composition according to any one of embodiments 13 to 16, wherein the ionic conductivity of the composition at 25°C is 0.01 mS / cm or more when measured by electrochemical impedance spectroscopy.

[0136] Embodiment 18 The composition is Li 0 / Li + A composition according to any of embodiments 13 to 17, having a decomposition initiation current of 4.5 volts or more relative to [the specified value].

[0137] Embodiment 19 The composition according to any one of embodiments 13 to 18, wherein the composition has a lithium salt content of 20% to 80% by weight based on total weight.

[0138] Embodiment 20 A film, filament, nonwoven web, or fabric comprising any of the compositions of Embodiments 13 to 19.

[0139] Embodiment 21 A solid-state battery comprising a solid anode, a solid cathode, and a solid metal ion conductive separator sandwiched between the solid anode and the solid cathode, wherein at least one of the solid anode and the solid metal ion conductive separator contains a component having the composition of any of embodiments 13 to 19.

[0140] Embodiment 22 A solid lithium-ion battery comprising a solid anode capable of inserting and removing lithium ions, a solid cathode capable of inserting and removing lithium ions, and a solid lithium-ion conductive separator sandwiched between the anode and the cathode, wherein at least one of the solid anode, solid cathode, and solid separator contains a component having the composition of Embodiment 15.

[0141] Embodiment 23 A solid lithium-ion battery of Embodiment 22, wherein the solid lithium-ion conductive separation unit comprises the composition, and the lithium salt is selected from the group consisting of lithium bis(trifluoromethanesulfonylamide) (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0142] Embodiment 24 A solid lithium-ion battery of Embodiment 22 or Embodiment 23, wherein the solid lithium-ion conductive separation unit further comprises (i) a polymer different from the copolymer, and (ii) at least one additive selected from the group consisting of clay, metal oxides, metal nitrides, and lithium-conducting ceramics.

[0143] Embodiment 25 A solid lithium-ion battery according to any of embodiments 22 to 24, wherein the solid lithium-ion conductive separation unit includes a lithium-conductive ceramic, and the lithium-conductive ceramic is selected from the group consisting of lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphate sulfur chloride (LSPSCl), lithium germanium phosphate sulfide (LGPS), lithium-conductive halide, closoborate, and nidoborate.

[0144] Embodiment 26 A solid lithium-ion battery according to any of embodiments 22 to 25, wherein the solid lithium-ion conductive separation portion is in the form of a film having a thickness of less than 30 microns, and the film has an ionic conductivity of 0.05 mS / cm or more.

[0145] Embodiment 27 A solid lithium-ion battery of Embodiment 22, wherein the solid anode comprises the composition, and the lithium salt is selected from the group consisting of lithium bis(trifluoromethanesulfonylamide) (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0146] Embodiment 28 A solid lithium-ion battery of Embodiment 22, wherein the solid cathode contains the composition, and the lithium salt is selected from the group consisting of lithium bis(trifluoromethanesulfonylamide) (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF2(C2O4), LiC2O4, CF3CO2Li, and C6H5COOLi.

[0147] Embodiment 29 A solid lithium-ion battery according to any of embodiments 22 to 28, wherein the at least one additional monomer does not contain an epoxy group and is not formed from a compound containing an epoxy group.

[0148] Embodiment 30 A method for preparing a copolymer according to any one of Embodiments 1 to 12, comprising: dissolving the vinylene carbonate compound in a solvent; contacting the 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 to obtain a copolymer in a reaction mixture; precipitating the copolymer from the reaction mixture under conditions effective for precipitating the polymer; and isolating the copolymer from the reaction mixture.

[0149] Embodiment 31 The method of Embodiment 30, wherein the solvent is dimethyl sulfoxide, tetrahydrofuran, or N-methyl-2-pyrrolidone.

[0150] Embodiment 32 The method of Embodiment 30 or Embodiment 31, wherein the polymerization initiator is 2,2'-azobis(2,4-dimethylvaleronitrile).

[0151] Embodiment 33 A method according to any of Embodiments 30 to 32, wherein the reaction conditions sufficient for copolymerizing the vinylene carbonate compound with the at least one additional monomer include a temperature of 40°C to 100°C.

[0152] Embodiment 34 The method according to any of embodiments 30 to 33, wherein the method has a copolymer yield of more than 50%.

[0153] Embodiment 35 A film comprising a polymer containing a first monomer of vinylene carbonate and a second monomer different from the first monomer but without a glycidyl group, wherein the molar ratio of the first monomer to the at least one additional monomer is 4:1 to 99:1.

[0154] Embodiment 36 The film of Embodiment 35 further contains a metal salt, has a thickness of less than 30 microns, and has an ionic conductivity of 0.05 mS / cm or more.

[0155] Embodiment 37 A separation section including the conductive film of embodiment 36.

[0156] Embodiment 38 A conductive layer within an electrode, comprising the conductive film of embodiment 36.

[0157] While exemplary and currently preferred embodiments of the disclosed methods, separation units, and batteries are described in detail herein, it should be understood that the concepts of the present invention can be carried out and adopted in a variety of other forms. Furthermore, the appended claims are intended to be construed to include such modifications unless limited by the prior art.

[0158] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as they are commonly or conventionally understood. Where used herein, the article “one” refers to one or more (i.e., at least one) of the grammatical objects of that article. For example, “one element” means one element or two or more elements. Where used herein, “about” and / or “approximately” refers to measurable values ​​such as quantities and durations, and where appropriate in the context of the systems, apparatus, circuits, methods, and other implementations described herein, includes variations of ±20%, ±10%, ±5%, or ±0.1% from the specified value. Where used herein, “substantially” refers to measurable values ​​such as quantities, durations, and physical characteristics (such as frequency), and also includes variations of ±20%, ±10%, ±5%, or +0.1% from the specified value, where appropriate in the context of the systems, apparatus, circuits, methods, and other implementations described herein. If an element of a claim is described as being "selected from the group consisting of ~", followed by a list of configurations, the element may be selected from one or any combination of these alternative configurations.

[0159] Where a range of values ​​is indicated, unless otherwise explicitly stated in the context, each intermediate value between the upper and lower limits of that range (up to the smallest unit fraction of the lower limit) is understood to be specifically disclosed. This also includes narrower ranges between the explicitly stated or unexpressed intermediate values ​​within the stated range and other explicitly stated or intermediate values ​​within that range. The upper and lower limits of these narrower ranges may be independently included in or excluded from that range, and each range that does not include either, neither, or both limits within a smaller range is also included in the Art, subject to the limits explicitly excluded within the stated range. Where the stated range includes one or both limits, it also includes ranges that exclude one or both of the included limits.

[0160] In this specification (including the claims), the "and" used in lists of items beginning with "at least one" or "one or more" indicates that any combination of the enumerated items may be used. For example, the list "at least one of A, B, and C" includes any combination of A, B, C, AB, AC, BC, and / or ABC (i.e., A, B, and C). Furthermore, to the extent that items A, B, or C may appear or be used multiple times, multiple uses of A, B, and / or C may form part of the assumed combinations. For example, the list "at least one of A, B, and C" may also include AA, AAB, AAA, BB, etc.

Claims

1. As copolymerization units, A vinylene carbonate compound as the first monomer, and A copolymer comprising at least one additional monomer that is different from the first monomer and copolymerizable with the first monomer, wherein the at least one additional monomer does not contain a glycidyl group, A copolymer in which the molar ratio of the first monomer to the at least one additional monomer is 4:1 to 99:

1.

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

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

4. The at least one additional monomer is poly(ethylene glycol) methacrylate (PEGMA), 1,3-propensultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylethylene carbonate (VEC), dimethyl vinyl phosphonate (DMVP), maleic anhydride (MA), diethyl vinyl phosphonate (DEVP), diethyl allyl phosphonate (DEAP), or N-vinylpyrrolidone (NVP), N-methylmaleimide, vinylene sulfate, vinylene sulfite, vinylethylene sulfite, or butadiene sulfone, vinyl sulfonic acid (VSA). A copolymer of any of the claims, selected from the group consisting of N,N-dimethylvinylsulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphosphoran-2-oxide, metallic vinyl sulfonate, metallic vinyl phosphonate, metallic fluoro(vinyl)phosphinate, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metallic trifluoro(vinyl)boronate, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metallic 2-fluoro-2-vinyl-1,3,2-dioxaborolate-4,5-dione.

5. The at least one additional monomer is poly(ethylene glycol) methacrylate (PEGMA), 1,3-propensultone (PES), bis(2,2,2-trifluoroethyl) maleate (TFM), vinylethylene carbonate (VEC), dimethyl vinyl phosphonate (DMVP), maleic anhydride (MA), diethyl vinyl phosphonate (DEVP), diethyl allyl phosphonate (DEAP), or N-vinylpyrrolidone (NVP), N-methylmaleimide, vinylene sulfate, vinylene sulfite, vinylethylene sulfite, or butadiene sulfone, vinyl sulfonic acid (VSA), N,N-dimethyl vinyl A copolymer according to any one of claims 1 to 4, comprising two distinct additional monomers selected from the group consisting of sulfonamide, vinylsulfonyl fluoride, fluoro(vinyl)phosphinic acid, vinylphosphonic acid, 2-vinyl-1,3,2-dioxaphosphoran-2-oxide, metallic vinyl sulfonate, metallic vinyl phosphonate, metallic fluoro(vinyl)phosphinate, 1-vinylpyrrolidine-2,5-dione, vinylboronic acid, metallic trifluoro(vinyl)boronate, 2-vinyl-1,3,2-dioxaborolane-4,5-dione, and metallic 2-fluoro-2-vinyl-1,3,2-dioxaborolate-4,5-dione.

6. The copolymer according to any one of claims 1 to 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 according to any of the claims, wherein the copolymer is not crosslinked.

8. The copolymer has a molecular weight exceeding 50,000 Da and a concentration of 0.5 g / cm³. 3 ~2.5 g / cm³ 3 A copolymer according to any of the claims, having a density of

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

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

11. The copolymer according to any of the claims, wherein the copolymer has a molecular weight exceeding 80,000 Da.

12. The copolymer according to any of the claims, wherein 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 any copolymer and metal salt of the above claims.

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

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

16. The lithium salt is selected from the group consisting of lithium bis(trifluoromethanesulfonylamide) (LiTFSa), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF ６ , LiBF ２ (C ２ O ４ ), LiC ２ O ４ , CF ３ CO ２ Li, and C ６ H ５ OLi, and the composition of claim 15 selected from the group consisting of

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

18. The composition is Li ０ / Li + A composition according to any one of claims 13 to 17, having a decomposition initiation current of 4.5 volts or more relative to [the specified substance].

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

20. A film, filament, nonwoven web, or fabric comprising any composition of claims 13 to 19.

21. solid anode, Solid cathode, and A solid metal ion conductive separation section sandwiched between the solid anode and the solid cathode. A solid-state battery comprising, A solid-state battery in which at least one of the solid anode and the solid metal ion conductive separation unit contains a component having a composition of any of claims 13 to 19.

22. A solid anode capable of inserting and removing lithium ions. A solid cathode capable of inserting and removing lithium ions, A solid lithium-ion battery comprising a solid lithium-ion conductive separator sandwiched between the anode and the cathode, A solid lithium-ion battery in which at least one of the solid anode, solid cathode, and solid isolation unit contains a component having the composition of claim 15.

23. The solid lithium ion conductive separation unit contains the composition, and the lithium salt is lithium bis(trifluoromethanesulfonylamide) (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF ６ LiBF ２ (C ２ O ４ ), LiC ２ O ４ CF ３ CO ２ Li, and C ６ H ５ A solid lithium-ion battery according to claim 22, selected from the group consisting of COOLi.

24. The solid lithium-ion battery according to claim 22 or 23, wherein the solid lithium-ion conductive separation unit further comprises (i) a polymer different from the copolymer, and (ii) at least one additive selected from the group consisting of clay, metal oxides, metal nitrides, and lithium-conducting ceramics.

25. A solid lithium-ion battery according to any one of claims 22 to 24, wherein the solid lithium-ion conductive separation unit includes a lithium-conductive ceramic, and the lithium-conductive ceramic is selected from the group consisting of lithium aluminum titanium phosphate (LATP), lithium lanthanum zirconium oxide (LLZO), lithium silicon phosphate sulfur chloride (LSPSCl), lithium germanium phosphate sulfide (LGPS), lithium-conductive halide, closoborate, and nidoborate.

26. The solid lithium-ion battery according to any one of claims 22 to 25, wherein the solid lithium-ion conductive separation portion is in the form of a film having a thickness of less than 30 microns, and the film has an ionic conductivity of 0.05 mS / cm or more.

27. The solid anode comprises the composition, wherein the lithium salt is lithium bis(trifluoromethanesulfonylamide) (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF6, LiBF ２ (C ２ O ４ ), LiC ２ O ４ CF ３ CO ２ Li, and C ６ H ５ A solid lithium-ion battery according to claim 22, selected from the group consisting of COOLi.

28. The solid cathode comprises the composition, and the lithium salt is lithium bis(trifluoromethanesulfonylamide) (LiTFSA), lithium bis(oxalato)borate (LiBOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiPF ６ LiBF ２ (C ２ O ４ ), LiC ２ O ４ CF ３ CO ２ Li, and C ６ H ５ A solid lithium-ion battery according to claim 22, selected from the group consisting of COOLi.

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

30. Dissolving the vinylene carbonate compound in one solvent, In the aforementioned solvent, under reaction conditions sufficient to copolymerize the vinylene carbonate compound with the at least one additional monomer, the at least one additional monomer is brought into contact with the vinylene carbonate compound and one polymerization initiator to obtain a copolymer in the reaction mixture. Precipitating the copolymer from the reaction mixture under conditions effective for precipitating the polymer, and To isolate the copolymer from the reaction mixture. A method for producing any copolymer of claims 1 to 12, including the above.

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 according to any one of claims 30 to 32, wherein the reaction conditions sufficient for copolymerizing the vinylene carbonate compound with the at least one additional monomer include a temperature of 40°C to 100°C.

34. The method described above, wherein the copolymer yield is greater than 50%, according to any one of claims 30 to 33.

35. A film comprising a polymer containing a first monomer of vinylene carbonate and a second monomer different from the first monomer but without a glycidyl group, wherein the molar ratio of the first monomer to the at least one additional monomer is 4:1 to 99:

1.

36. The film according to claim 35, further comprising a metal salt, having a thickness of less than 30 microns, and having an ionic conductivity of 0.05 mS / cm or more.

37. A separation unit comprising the conductive film of claim 36.

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

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