Spirobisindan copolymer and method of manufacture

Abstract

This invention describes intrinsically microporous spirobisindan and spirobischroman copolymers for use as separators in electrochemical cells.

Description

[Technical Field]

[0001] Cross-references to related applications This application claims priority to U.S. Provisional Application No. 63 / 510,978, filed on 29 June 2023, which is incorporated herein by reference in its entirety for all purposes. [Background technology]

[0002] Over the past several decades, lithium-ion batteries (Li-ion batteries) have developed as the dominant high-energy chemistry due to their unparalleled high energy density while maintaining high output and cycleability at an acceptable price. However, the energy density of currently available Li-ion battery chemistry is approaching the theoretical limits of the technology, while the rapid trend toward electrification of the transportation and energy industries is increasing the demand for batteries with higher energy density at lower unit costs. In fact, there is a need for batteries with improved capacity, longer cycle life, and high stability. Replacing the graphite anode in Li-ions with a lithium metal anode offers an opportunity to significantly increase the energy density of lithium batteries. However, after repeated charge-discharge cycles, lithium metal batteries suffer irreversible capacity loss caused by electrolyte depletion and loss of lithium stock due to parasitic reactivity between the highly reactive lithium metal anode and the electrolyte component. This process contributes to localized heterogeneity on the lithium anode surface, further propagating uneven plating and delamination, resulting in physically isolated "dead" lithium. Furthermore, uneven lithium plating increases the risk of dendritic crystal formation, potentially leading to thermal runaway and catastrophic cell failure, posing a significant obstacle to the commercialization of lithium metal batteries. Mitigating dendritic crystal formation in lithium metal batteries is crucial for their safe and stable use in commercial applications.

[0003] The battery separator is a crucial component of lithium-ion batteries, separating electrodes, transporting ions through large pores filled with electrolyte, and insulating against electronic conductivity that would otherwise induce short circuits. While separators do not directly participate in cell reactions, their physical properties play a vital role in determining battery performance, including energy density, power density, and safety. Importantly, the mechanical integrity of the separator throughout the entire lifespan of the battery cell is critical to preventing internal short circuits.

[0004] Currently, several porous membrane separator materials and composites are used in lithium-ion batteries, including separators made from polyolefins, such as polyethylene (PE), polypropylene (PP), and polypropylene-polyethylene-polypropylene (PP / PE / PP), and ceramic-coated separators containing PP, PE, or multilayer porous substrates having at least one surface coated with a ceramic composite layer. As described in U.S. Patent No. 6,432,583 (Celgard Inc.), the ceramic composite layer is intended to inhibit dendritic crystal growth and prevent electron short circuits. While ceramic-coated separators have been successfully used in lithium-ion batteries to improve mechanical properties, their usefulness is limited in lithium metal batteries due to parasitic reactions induced at the anode by the binding material hosting the ceramic coating.

[0005] International Publication No. 2018 / 106957 (Sepion Technologies, Inc. et al.) describes the application of a porous polymer (10-40% porosity, 0.5-2.0 nm pores) as a template for delivering a solution-treated precursor of a solid-state halide-containing salt as a conformal coating between the Li metal surface and the separator surface to increase the wettability of the separator and increase the concentration and mobility of Li ions at the separator-anode interface. The document also describes an electrochemical cell including a separator comprising several layers, such as a first polymer layer containing planar seeds and a linker. The separator may also include a porous support made of PP or PE laminated onto the first polymer layer. The separator may also include a second film layer laminated onto the porous support, such a second layer comprising a ceramic material.

[0006] The use of intrinsically microporous polymers (PIMs) as selective battery membranes has been studied. PIMs consist of condensed rings that provide rigid and torsional regions, which may be provided by spirocenters, bent or bridged ring portions, or similar structural components that act as barriers preventing conformational relaxation of polymer chains. PIMs have been described and studied since 2006 because they create a continuous network of interconnected voids that can be used as gas separation membranes, hydrogen storage materials, adsorbents, and heterogeneous catalysts. The intrinsic microporosity of PIMs is defined as a continuous network of interconnected intermolecular voids formed as a direct result of the shape and rigidity of the component polymers. Notably, the paper by Li et al. (Nano Lett. 2015, 15, 5724-5729) describes the use of PIMs as a membrane platform to achieve high-flux ion-selective transport in non-aqueous electrolytes.

[0007] Because lithium metal is highly reactive, a solid electrolyte interface phase (SEI) is formed at the interface between the electrode and the adjacent electrolyte-filled separator. The composition and morphology of the SEI affect the performance of the electrochemical cell. On the one hand, the consumption of some lithium stock inherent in the in-situ SEI formation process reduces the Coulombic efficiency of the electrochemical cell. On the other hand, an optimal SEI limits further decomposition of electrolyte components, improves lithium ion transport at the electrode-separator interface, and improves the battery's cycle performance and lifespan.

[0008] Artificial SEI layers have been studied to limit the depletion process of lithium stock and electrolyte components on the surface of anode materials. One method is based on the use of a layer of PIM coated on a porous support. In particular, International Publication No. 2020 / 037246(A1) (The Regents of the University of California) describes a microporous ladder polymer represented by formula -[A-AB-B], comprising amine-functionalized monomer segments, amidooxime-functionalized monomer segments, or combinations thereof, and such a microporous polymer is used in separators which may include one or more support materials such as glass fibers. Examples describe thin films of microporous polymers on porous supports such as polyolefin battery separators (e.g., Celgard). A paper by Chengyin Fu et al. (Nature Materials, April 2020) describes a lithium electrode in which a TBAF@PIM-1 coated polyolefin separator, i.e., a separator coated with a microporous polymer host (e.g., PIM-1) in combination with a separator (Celgard 2325), is laminated together with the separator. The coated separator is then assembled into either a Li-Li or Li-NMC-622 cell with a carbonate electrolyte containing an ionizable lithium salt (e.g., LiPF6). The composite is described as acting as a dendritic crystal suppression solid ion conductor (SIC) in lithium metal batteries. What is needed is a novel polymer for the separator coating. Surprisingly, the present invention meets this and other requirements. [Overview of the project]

[0009] In one embodiment, the present invention provides a copolymer comprising a plurality of repeating units A and B. A and B are independent of each other, Equation I [ka] Structure or formula II [ka] It is a repeating unit having the structure of, A and B are different from each other, R , 1d , 1b1 , 1c , 1-6 , 2-6 , 1-6 , 1d , 1a1 , 2-6 , 2-6 and R 1b are, independently of each other, hydrogen, C 1-6 alkyl, halogen, C 1-6 haloalkyl, -CH2R 1c or NR 1a1 R 1b1 and each R 1a1 and R 1b1 are, independently, hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 hydroxyalkyl, C 2-6 alkoxyalkyl, C 1-6 alkyl-NR 1a2 R 1b2 C 3-10 cycloalkyl or C 1-6 alkyl-C 3-10 cycloalkyl and [[ID=5l]]each R 1a2 and R 1b2 are independently hydrogen or C 1-6 alkyl and each R 1c is, independently, NR 1a1 R 1b1 a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms (each independently N, O or S), or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms (each independently N, O or S), provided that the heterocycloalkyl and heteroaryl are each independently substituted with 0, 1, 2, 3, 4 or 5 R 1d groups and each R 1d is, independently, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 hydroxyalkyl, C 2-6 alkoxyalkyl, halogen, C1-6 Haloalkyl, -OH, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1e , -C(O)OR 1e -S(O)2R 1e , -C 1-6 Alkyl-(SO3 - ), -OP(=O)(OR 1e ) A heterocycloalkyl group of 3 to 10 members having 2,1 to 4 heteroatoms (each independently N, O, or S), or a heteroaryl group of 3 to 10 members having 1 to 4 heteroatoms (each independently N, O, or S), R 1e is C 1-6 Alkyl or C 1-6 It is a hydroxyalkyl, R 2a and R 2b These are, independently, hydrogen and C 1-6 Alkyl, halogen, C 1-6 Haloalkyl, -CH2R 2c or NR 2a1 R 2b1 And, Each R 2a1 and R 2b1 These are, independently, hydrogen and C 1-6 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Hydroxyalkyl, C 2-6 Alkoxyalkyl, C 1-6 Alkyl-NR 2a2 R 2b2 , C 3-10 Cycloalkyl or C 1-6 Alkyl-C 3-10 It is a cycloalkyl, Each R 2a2 and R 2b2 These are, independently, hydrogen or C 1-6 It is alkyl, Each R 2c NR is independent. 2a1 R 2b1, a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms (each independently N, O, or S), or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms (each independently N, O, or S), provided that the heterocycloalkyl and heteroaryl are each independently substituted with 0, 1, 2, 3, 4, or 5 R 2d groups, each R 2d is independently C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 hydroxyalkyl, C 2-6 alkoxyalkyl, halogen, C 1-6 haloalkyl, -OH, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 2e , -C(O)OR 2e [ , -S(O)2R 2e , -C 1-6 alkyl-(SO3 - ), -OP(=O)(OR 2e )2, a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms (each independently N, O, or S), or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms (each independently N, O, or S), R 2e is C 1-6 alkyl or C 1-6 hydroxyalkyl, X is -N= or -C(R 3b )=, each R 3a and R 3b are independently hydrogen, C 1-6 alkyl, halogen, C 1-6 haloalkyl, -CN or -S(O)2R 3c , and, each R 3c is independently C 1-6 alkyl, C 1-6 haloalkyl or C 6-12Aryl, provided that each aryl is independently substituted with 0, 1, 2, 3, 4 or 5 groups (each independently C 1-6 alkyl or C 1-6 haloalkyl).

[0010] In another embodiment, the present invention provides a coated separator comprising a porous membrane support and a membrane layer comprising the copolymer of the present invention on the porous membrane support.

[0011] In another embodiment, the present invention provides an electrochemical cell comprising an anode, a cathode, the separator of the present invention, and an electrolyte. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] [Figure 1] FIG. 1 shows the effect of copolymer composition on the proportion of polymer dissolved in the E1 electrolyte from a 14 mg / mL mixture of the polymer in E1.

[0013] [Figure 2] FIGS. 2A and 2B show the coated separator and the multilayer coated separator of the present invention.

[0014] [Figure 3] FIGS. 3A and 3B show the electrochemical cell of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] I. DEFINITIONS The abbreviations used herein have their conventional meanings within the scope of chemical and biological arts.

[0016] When substituents are specified by their conventional chemical formulas written from left to right, they equally encompass the chemically identical substituents that would result when the structure is written from right to left; for example, -CH2O- is equivalent to -OCH2-.

[0017] A "copolymer" is a polymer that contains at least two different repeating units. The two different repeating units can be irregularly distributed in the polymer chain to form a random copolymer in which the repeating units are irregularly located in the polymer chain, or they can be organized into different blocks of repeating units to form a block copolymer (e.g., AAAABBBBBAAA). Copolymers also include alternating copolymers (ABABABAB) in which the repeating units are arranged alternately in the copolymer chain.

[0018] "Molecular weight" refers to the molecular weight of a polymer determined by size exclusion chromatography (SEC), laser light scattering, MALDI-TOF, or other methods. Molecular weight can be measured by weight average or number average. "Number average molecular weight" (M N ) refers to the mole fraction of molecules in a polymer sample, that is, the value obtained by dividing the total weight of the polymer by the total number of molecules, i.e., the arithmetic mean. "Weight-average molecular weight" (M W ) refers to the weight fraction of molecules in a polymer sample, M W M N The weights of individual molecules are emphasized to make the result larger than M. W / M N The polydispersity index, which is the ratio of molecular weights, represents the distribution of molecular weights within the polymer.

[0019] "Alkyl" refers to the number of carbon atoms indicated (i.e., C 1-6 A C1 means 1 to 6 carbon atoms. A alkyl group is a linear or branched saturated aliphatic group having 1 to 6 carbon atoms. 1―2 , C 1―3 , C 1―4 , C 1―5 , C 1―6 , C 1―7 , C 1―8 , C 1―9 , C 1―10 , C 2―3 , C 2―4 , C 2―5 , C 2―6 , C 3―4 , C 3―5 , C 3―6 , C 4―5 , C 4―6and C 5―6 It can contain any number of carbon atoms, such as C. 1―6 Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0020] "Alkenyl" is defined as having at least two carbon atoms and at least one double bond, and the indicated number of carbon atoms (i.e., C 2-6 C2 means 2 to 6 carbon atoms. ) refers to a straight-chain or branched hydrocarbon having 2 to 6 carbon atoms. Alkenyls are C2, 2―3 , C 2―4 , C 2―5 , C 2―6 , C 2―7 , C 2―8 , C 2―9 , C 2―10 , C3, C 3―4 , C 3―5 , C 3―6 , C4, C 4―5 , C 4―5 , C5, C 5―6 and can contain any number of carbon atoms, such as C6. The alkenyl group can have any suitable number of double bonds (including, but not limited to, 1, 2, 3, 4, 5 or more). 2-4 Examples of alkenyl groups include, but are not limited to, vinyl (ethenyl), propenyl, isopropenyl, 1-butenyl, 2-butenyl, isobutenyl, or butadienyl.

[0021] "Alkynyl" means having at least two carbon atoms and at least one triple bond, and the indicated number of carbon atoms (i.e., C 2-6 Alkynnyl refers to a straight-chain or branched hydrocarbon having 2 to 6 carbon atoms. 2-3 , C 2-4 , C 2-5 , C 2-6 , C 2-7 , C 2-8 , C 2-9 , C 2-10 , C3, C3-4 , C 3-5 , C 3-6 , C4, C 4-5 , C 4-6 , C5, C 5-6 It can also include any number of carbon atoms, such as C6. 2-4 Examples of alkynyl groups include, but are not limited to, acetylenyl, propynyl, 1-butynyl, 2-butynyl, isobutynyl, sec-butynyl, or butadiinyl.

[0022] "Hydroxyalkyl" or "alkylhydroxy" refers to the alkyl group defined above, in which at least one hydrogen atom is substituted with a hydroxyl group. Regarding alkyl groups, a hydroxyalkyl group or alkylhydroxy group is C 1―6 It can have any appropriate number of carbon atoms, such as C. 1-4 Examples of hydroxyalkyl groups include, but are not limited to, hydroxymethyl, hydroxyethyl (where the hydroxyl group is at the 1- or 2-position), hydroxypropyl (where the hydroxyl group is at the 1-, 2-, or 3-position), hydroxybutyl (where the hydroxyl group is at the 1-, 2-, 3-, or 4-position), and 1,2-dihydroxyethyl.

[0023] "Alkyl-alkoxy" or "alkoxyalkyl" refers to a group having an alkyl component and an alkoxy component, where the alkyl component links the alkoxy component to its bonding site. The alkyl component is as defined above, except that it is at least divalent, i.e., alkylene, in order to link with the alkoxy component and the bonding site. The alkyl component is C 0-6 , C6, C 1-2 , C 1-3 , C 1-4 , C 1-5 , C 1-6 , C 2-3 , C 2-4 , C 2-5 , C 2-6 , C 3-4 , C 3-5 , C 3-6, C 4-5 , C 4-6 and C 5-6 It can contain any number of carbon atoms, such as those mentioned above. In some cases, the alkyl component may be absent. The alkoxy component is as defined above. Examples of alkyl-alkoxy groups include, but are not limited to, 2-ethoxyethyl and methoxymethyl.

[0024] "Halogens" refer to fluorine, chlorine, bromine, and iodine.

[0025] A "haloalkyl" is an alkyl group defined above in which some or all of the hydrogen atoms are replaced by halogen atoms. Regarding alkyl groups, haloalkyl groups are C 1―6 It can have any appropriate number of carbon atoms, such as trifluoromethyl, fluoromethyl, and 2,2,2-trifluoroethyl. In some cases, haloalkyl includes the term "fluoroalkyl," which can be used to define alkyl groups in which one or more hydrogens are substituted with fluorine.

[0026] A "cycloalkyl" is a saturated or partially unsaturated monocyclic, fused dicyclic, or bridged polycyclic ring assembly containing 3 to 12 ring atoms or the indicated number of atoms. 3-6 , C 4-6 , C 5-6 , C 3-8 , C 4-8 , C 5-8 , C 6-8 , C 3-9 , C 3-10 , C 3-11 and C 3-12It can contain any number of carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. Examples of saturated monocyclic cycloalkyl rings include norbornane, [2.2.2]bicyclooctane, decahydronaphthalene, and adamantane. Cycloalkyl groups may also be partially unsaturated and may have one or more double or triple bonds in the ring. Representative partially unsaturated cycloalkyl groups include, but are not limited to, cyclobutene, cyclopentene, cyclohexene, cyclohexadiene (1,3- and 1,4-isomers), cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene (1,3-, 1,4- and 1,5-isomers), norbornene, and norbornadiene. 3-8 When the group is cycloalkyl, exemplary groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. 3-6 If the group is cycloalkyl, exemplary groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The cycloalkyl group may be substituted or unsubstituted.

[0027] "Alkyl-cycloalkyl" refers to a group having an alkyl component and a cycloalkyl component, where the alkyl component links to the cycloalkyl component at its bonding site. The alkyl component is as defined above, except that it is at least divalent, i.e., alkylene, in order to link to the cycloalkyl component and the bonding site. In some cases, the alkyl component may not be present. The alkyl component is C 1-6 , C 1-2 , C 1-3 , C 1-4 , C 1-5 , C 2-3 , C 2-4 , C 2-5 , C C2-6 , C3-4 , C 3-5 , C 3-6 , C 4-5 , C 4-6 and C 5-6 It may contain any number of carbon atoms, such as those listed above. The cycloalkyl components are as defined herein. Examples of alkyl-cycloalkyl groups include, but are not limited to, methyl-cyclopropyl, methyl-cyclobutyl, methyl-cyclopentyl, and methyl-cyclohexyl.

[0028] A "heterocyclic ring" or "heterocycloalkyl" is a saturated ring system having 3 to 12 ring atoms and 1 to 4 N, O, and S heteroatoms. The heteroatoms may be oxidized, such as -S(O)- and S(O)2-, but are not limited to these. A heterocycloalkyl group can contain any number of ring atoms, such as 3 to 6, 4 to 6, 5 to 6, 3 to 8, 4 to 8, 5 to 8, 6 to 8, 3 to 9, 3 to 10, 3 to 11, or 3 to 12 ring atoms. A heterocycloalkyl group can contain any appropriate number of heteroatoms, such as 1, 2, 3, or 4, or 1 to 2, 1 to 3, 1 to 4, 2 to 3, 2 to 4, or 3 to 4. Examples of heterocycloalkyl groups include aziridine, azetidine, pyrrolidine, piperidine, azepane, azocane, quinuclidine, pyrazolidine, imidazolidine, piperazine (1,2-, 1,3-, and 1,4-isomers), oxirane, oxetane, tetrahydrofuran, oxane (tetrahydropyran), oxepane, thiirane, thiethane, thiolane (tetrahydrothiophene), thian (tetrahydrothiopyran), oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, dioxolane, dithiolane, morpholine, thiomorpholine, dioxane, or dithiane. Heterocycloalkyl groups may also be condensed into aromatic or non-aromatic ring systems to form rings containing indoline, but are not limited to these groups. Heterocycloalkyl groups may be unsubstituted or substituted. For example, a heterocycloalkyl group may be C 1-6 It can be substituted with various groups such as alkyl or oxo (=O).

[0029] "Alkyl-heterocycloalkyl" refers to a group having an alkyl component and a heterocycloalkyl component, where the alkyl component links the heterocycloalkyl component to a bonding site. The alkyl component is as defined above, except that it is at least divalent, i.e., alkylene, in order to bond to the heterocycloalkyl component and the bonding site. The alkyl component is C 0-6 , C 1-2 , C 1-3 , C 1-4 , C 1-5 , C 1-6 , C 2-3 , C 2-4 , C 2-5 , C 2-6 , C 3-4 , C 3-5 , C 3-6 , C 4-5 , C 4-6 and C 5-6 It can contain any number of carbon atoms, such as those listed above. In some cases, the alkyl component may be absent. The heterocycloalkyl component is as defined above. The alkyl-heterocycloalkyl group may be substituted or unsubstituted.

[0030] An "aryl" group is an aromatic ring system having any appropriate number of ring atoms and any appropriate number of rings. An aryl group can contain 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 ring atoms, as well as any appropriate number of ring atoms such as 6-10, 6-12, or 6-14 ring atoms. An aryl group may be monocyclic, condensed to form a bicyclic or tricyclic group, or linked by bonds to form a biaryl group. Representative aryl groups include phenyl, naphthyl, and biphenyl. Other aryl groups include benzyl with a methylene linkage. Some aryl groups, such as phenyl, naphthyl, or biphenyl, have 6-12 ring atoms. Other aryl groups, such as phenyl or naphthyl, have 6-10 ring atoms. Some other aryl groups, such as phenyl, have 6 ring atoms. An aryl group may be substituted or unsubstituted.

[0031] "Alkyl-aryl" refers to a group having an alkyl component and an aryl component, where the alkyl component links to the aryl component at a bonding site. The alkyl component is as defined above, except that it is at least divalent, i.e., alkylene, in order to link to the aryl component and the bonding site. The alkyl component is C 0-6 , C 1-2 , C 1-3 , C 1-4 , C 1-5 , C 1-6 , C 2-3 , C 2-4 , C 2-5 , C 2-6 , C 3-4 , C 3-5 , C 3-6 , C 4-5 , C 4-6 and C 5-6It can contain any number of carbon atoms, as shown above. In some cases, the alkyl component may be absent. The aryl component is as defined above. Examples of alkyl-aryl groups include, but are not limited to, benzyl and ethyl-benzene. The alkyl-aryl group may be substituted or unsubstituted.

[0032] A "heteroaryl" is a monocyclic, fused dicyclic, or tricyclic aromatic ring assembly containing 5 to 16 ring atoms, where 1 to 5 of the ring atoms are heteroatoms such as N, O, or S. The heteroatoms may be oxidized, but are not limited to N-oxides, -S(O)-, and -S(O)2-. The nitrogen atom may also be quaternized. A heteroaryl group can contain any number of ring atoms, such as 5 to 6, 5 to 8, 6 to 8, 5 to 9, 5 to 10, 5 to 11, or 5 to 12 ring atoms. A heteroaryl group can contain any appropriate number of heteroatoms, such as 1, 2, 3, 4, or 5, or 1 to 2, 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, 2 to 5, 3 to 4, or 3 to 5. A heteroaryl group can have 5 to 10 ring atoms and 1 to 4 heteroatoms, 5 to 8 ring atoms and 1 to 4 heteroatoms, 5 to 8 ring atoms and 1 to 3 heteroatoms, 5 to 6 ring atoms and 1 to 4 heteroatoms, or 5 to 6 ring atoms and 1 to 3 heteroatoms. Examples of heteroaryl groups include pyrrole, pyridine, imidazole, pyrazole, triazole, tetrazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiophene, furan, thiazole, isothiazole, oxazole, and isoxazole. Heteroaryl groups can also condense with aromatic ring systems, such as phenyl rings, to form aromatic compounds such as benzopyrroles (like indole and isoindole), benzopyridines (like quinoline and isoquinoline), benzopyrazines (like benzopyrazine (quinoxaline)), benzopyrimidines (quinazoline)), benzopyridazines (like phthalazine and cinnoline), benzothiophene, and benzofuran. Other heteroaryl groups include heteroaryl rings linked by bonds, such as bipyridines.

[0033] Heteroaryl groups can be linked at any position on the ring. For example, pyrrole contains 1-,2- and 3-pyrrole, pyridine contains 2-,3- and 4-pyridine, imidazole contains 1-,2-,4- and 5-imidazole, pyrazole contains 1-,3-,4- and 5-pyrazole, triazole contains 1-,4- and 5-triazole, tetrazole contains 1- and 5-tetrazole, pyrimidine contains 2-,4-,5- and 6-pyrimidine, pyridazine contains 3- and 4-pyridazine, 1,2,3-triazine contains 4- and 5-triazine, 1,2,4-triazine contains 3-,5- and 6-triazine, 1,3,5-triazine contains 2-triazine, thiophene contains 2- and 3-thiophene, and furan contains 2- 3-furans are included, thiazoles are included 2-, 4- and 5-thiazoles, isothiazoles are included 3-, 4- and 5-isothiazoles, oxazoles are included 2-, 4- and 5-oxazoles, isoxazoles are included 3-, 4- and 5-isoxazoles, indoles are included 1-, 2- and 3-indoles, isoindoles are included 1- and 2-isoindoles, quinolines are included 2-, 3- and 4-quinolines, isoquinolines are included 1-, 3- and 4-isoquinolines, quinazolines are included 2- and 4-quinazolines, sinnolines are included 3- and 4-sinnolines, benzothiophenes are included 2- and 3-benzothiophenes, and benzofurans are included 2- and 3-benzofurans.

[0034] Some heteroaryl groups include those having 5 to 10 ring-forming atoms and 1 to 3 ring atoms containing N, O, or S, such as pyrrole, pyridine, imidazole, pyrazole, triazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiophene, furan, thiazole, isothiazole, oxazole, isoxazole, indole, isoindole, quinoline, isoquinoline, quinoxaline, quinazoline, phthalazine, cinnoline, benzothiophene, and benzofuran. Other heteroaryl groups include those having 5 to 8 ring atoms and 1 to 3 heteroatoms, such as pyrrole, pyridine, imidazole, pyrazole, triazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiophene, furan, thiazole, isothiazole, oxazole, and isoxazole. Some other heteroaryl groups include those having 9 to 12 ring atoms and 1 to 3 heteroatoms, such as indole, isoindole, quinoline, isoquinoline, quinoxaline, quinazoline, phthalazine, cinnoline, benzothiophene, benzofuran, and bipyridine. Furthermore, other heteroaryl groups include those having 5-6 ring constituent atoms and 1-2 ring atoms containing N, O, or S, such as pyrrole, pyridine, imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, thiophene, furan, thiazole, isothiazole, oxazole, and isoxazole.

[0035] Some heteroaryl groups, such as pyrrole, pyridine, imidazole, pyrazole, triazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), indole, isoindole, quinoline, isoquinoline, quinoxaline, quinazoline, phthalazine, and cinnoline, contain only 5 to 10 ring-forming atoms and a nitrogen heteroatom. Other heteroaryl groups, such as furan and benzofuran, contain only 5 to 10 ring-forming atoms and an oxygen heteroatom. Some other heteroaryl groups, such as thiophene and benzothiophene, contain only 5 to 10 ring-forming atoms and a sulfur heteroatom. Furthermore, other heteroaryl groups, such as imidazole, pyrazole, triazole, pyrazine, pyrimidine, pyridazine, triazine (1,2,3-, 1,2,4-, and 1,3,5-isomers), thiazole, isothiazole, oxazole, isoxazole, quinoxaline, quinazoline, phthalazine, and cinnoline, contain 5 to 10 ring-forming atoms and at least 2 heteroatoms.

[0036] "Alkyl-heteroaryl" refers to a group having an alkyl component and a heteroaryl component, where the alkyl component links the heteroaryl component to a bonding site. The alkyl component is as defined above, except that it is at least divalent, i.e., alkylene, in order to link to the heteroaryl component and the bonding site. The alkyl component is C 0-6 , C 1-2 , C 1-3 , C 1-4 , C 1-5 , C 1-6 , C 2-3 , C 2-4 , C 2-5 , C 2-6 , C 3-4 , C 3-5 , C 3-6 , C 4-5 , C 4-6 and C 5-6It can contain any number of carbon atoms, such as those mentioned above. In some cases, the alkyl component may be absent. The heteroaryl component is as defined herein. The alkyl-heteroaryl group may be substituted or unsubstituted.

[0037] "Salt" refers to an acid acid or base salt of a compound used in the method of the present invention. The salts of basic compounds in the present invention are salts formed together with acids such as mineral acids, organic carboxylic acids, and organic sulfonic acids. Examples of salts include, but are not limited to, halogen salts such as fluoride salts, chloride salts, bromide salts, and iodide salts; oxanion salts such as chlorates, bromates, iodates, carbonates, nitrates, sulfates, or phosphates; carboxylate salts such as fumarates or acetates; and sulfonates such as trifluoromethylsulfonates.

[0038] Furthermore, as long as an acidic group constitutes part of the structure, base addition salts, such as sodium salts, potassium salts, calcium salts, ammonium salts, organic amino salts, or magnesium salts, or similar salts, are also included. Specific examples of salts include mineral acid salts (hydrochloric acid, hydrobromic acid, phosphoric acid, etc.), organic acid salts (acetic acid, propionic acid, glutamic acid, citrate, etc.), and quaternary ammonium salts (methyl iodide, ethyl iodide, etc.).

[0039] "Sulfonate" refers to -S(O)3 - This refers to compounds containing [a specific compound]. An example of a sulfonate is H3C-S(O)3 - H3CCH2-S(O)3 - Or F3C-S(O)3 - These include, but are not limited to, sulfonates, which are formed by a single bond of -S(O)3 - It can contain any chemical group bonded to it.

[0040] A "carbonate" is a compound of the formula R′OC(O)OR″, where R′ and R″ may be the same, different, or bonded to form a cyclic structure. R′ and R″ may be alkyl, haloalkyl, or bonded to form an alkylene, and the alkylene may optionally be substituted with a halogen. Representative carbonates include, but are not limited to, dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC).

[0041] "Forming a reaction mixture" refers to the process of bringing at least two different species into contact so that they can be mixed and reacted together. However, it should be understood that the resulting reaction product may be produced directly from the reaction between the added reagents, or from intermediates formed from one or more of the added reagents in the reaction mixture.

[0042] A "solvent" is a substance, such as a liquid, that can dissolve a solute. A solvent may be polar or nonpolar, and may be protic or aprotic. Polar solvents typically have a dielectric constant greater than about 5 or a dipole moment less than about 1.0. Protic solvents are characterized by having removable protons, for example, by having a hydroxyl group or a carboxyl group. Aprotic solvents lack such groups. Typical polar protic solvents include alcohols (methanol, ethanol, propanol, isopropanol, etc.), acids (formic acid, acetic acid, etc.), and water. Typical polar aprotic solvents include dichloromethane, chloroform, tetrahydrofuran, diethyl ether, acetone, ethyl acetate, dimethylformamide, dimethylacetamide, acetonitrile, and dimethyl sulfoxide. Typical nonpolar solvents include alkanes (pentane, hexane, etc.), benzene, toluene, and 1,4-dioxane. Other solvents are useful in the present invention.

[0043] An "electrode" refers to a conductive material within a circuit that comes into contact with a non-metallic part of the circuit, such as an electrolyte. The electrode may be a positive electrode, or cathode, where reduction occurs. The electrode may also be a negative electrode, or anode, where oxidation occurs.

[0044] As mentioned above, the "anode" refers to the negative electrode.

[0045] As mentioned above, "cathode" refers to the positive electrode.

[0046] An "electrolyte" refers to the solution of an electrochemical cell that contains metal ions, protons, anions, and other ions, and provides ion transport between the positive and negative electrodes.

[0047] An "electrolyte solvent" is a molecule that solvates ions in a liquid electrolyte, such as a small organic carbonate or etheric molecule, which allows for the diffusion of ions in the electrolyte. Electrolyte solvents may also be ionic liquids or gases at standard temperature and pressure.

[0048] A "separator" is an electrically insulating film between the positive and negative electrodes that prevents electrical short circuits, i.e., provides electronic insulation. The separator also allows ions to move between the positive and anode electrodes. The separator can include any suitable polymer or inorganic material that is electrically insulating. The separator can include several layers, including one or more film layers and a porous support material for the film layers.

[0049] The “first polymer layer” refers to a separator layer that is permeable to the first species of electrolyte but substantially impermeable to the liquid electrolyte. The membrane layer may consist of any suitable material that can provide selective permeability, such as a composite of a microporous polymer and an inorganic material. “Substantially impermeable” means that less than 10% of the electrolyte solvent passes through the membrane layer, or less than 1%, 0.1%, 0.01%, or 0.001% of the liquid electrolyte passes through the membrane layer.

[0050] "Oxide" refers to compounds containing oxygen, such as metal oxides or molecular oxides.

[0051] "Pore size" or "pore diameter" refers to the average diameter of the void space not occupied by the pore-forming material. This may include, but is not limited to, spaces remaining between polymer chains due to inefficient packing, spaces remaining between organic linkers and metal ions in metal-organic frameworks, spaces between layers and within pores in laminated 2D materials, and spaces remaining in amorphous or semi-crystalline carbon due to misaligned covalent bonding. Pore size may also change or remain the same when wetted with an electrolyte.

[0052] "Surface area" refers to the surface area of ​​a porous material, measured by various methods such as nitrogen adsorption BET.

[0053] A "microporous polymer" refers to an amorphous, glassy polymer having interconnected pores with an average diameter of less than 10 nm, or less than 5, 4, 3, 2 nm, or 1 nm.

[0054] "Microporous" refers to a film layer containing pores with a size of 2 nm or less.

[0055] "Intrinsic microporosity" refers to a polymer that provides a continuous network of interconnected (preferably 4 nm in size or less) intermolecular voids, formed as a direct result of the shape and rigidity of at least some of the polymer's constituent monomers. As will be understood by those skilled in the art, intrinsic microporosity arises from the structure of the monomers used to form the polymer, and as the term suggests, it is an inherent property of polymers formed from such monomers.

[0056] It is understood that the network polymers disclosed herein have certain properties (i.e., intrinsic microporosity). Disclosed herein are specific structural requirements in monomers used to give polymers that perform the disclosed functions, and it is understood that various structures exist that can perform the same functions as the disclosed monomer structures, and these structures would typically achieve the same results.

[0057] A "metal" is an element of the periodic table that is metallic and neutral, or can be negatively or positively charged as a result of having more or fewer electrons in its valence shell than a neutral metallic element. Useful metals in this invention include alkali metals, alkaline earth metals, transition metals, and post-transition metals. Examples of alkali metals include Li, Na, K, Rb, and Cs. Examples of alkaline earth metals include Be, Mg, Ca, Sr, and Ba. Examples of transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and Ac. Examples of post-transition metals include Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, and Po. Examples of rare earth metals include Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Those skilled in the art will understand that each of the above metals can exist in several different oxidation states, all of which are useful in the present invention. In some cases, the most stable oxidation state is formed, but other oxidation states are also useful in the present invention.

[0058] "Porous support" refers to any suitable material that can support the film layer of the present invention and is permeable to electrolytes.

[0059] "Lamination" refers to placing one layer on top of another, such as placing a microporous polymer layer or a first polymer layer on top of a porous support.

[0060] II. Copolymer The present invention provides a copolymer of spiro-bisindane and / or spiro-bischromane monomer repeating units. In some embodiments, the present invention provides a copolymer comprising a plurality of repeating units A and B. However, A and B are each independently a repeating unit having the structure of Formula I [Chemical formula] or the structure of Formula II [Chemical formula] and A and B are different from each other, R 1a and R 1b are each independently hydrogen, C 1-6 alkyl, halogen, C 1-6 haloalkyl, -CH2R 1c or NR 1a1 R 1b1 R 1a1 and each R and R 1b1 are independently hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 hydroxyalkyl, C 2-6 alkoxyalkyl, C 1-6 alkyl-NR 1a2 R 1b2 R 3-10 cycloalkyl or C 1-6 alkyl-C 3-10 cycloalkyl, each R 1a2 and R 1b2 are independently hydrogen or C 1-6 alkyl, each R 1c is independently NR 1a1 R 1b1 R 1d, a 5- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms (each independently N, O or S), or a 5- to 10-membered heteroaryl having 1 to 4 heteroatoms (each independently N, O or S), provided that the heterocycloalkyl and heteroaryl are each independently substituted with 0, 1, 2, 3, 4 or 5 R 1d groups, each R 1d is independently C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 hydroxyalkyl, C 2-6 alkoxyalkyl, halogen, C 1-6 haloalkyl, -OH, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 1e , -C(O)OR 1e , -S(O)2R 1e , -C 1-6 alkyl-(SO3 - ), -OP(=O)(OR 1e ), a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms (each independently N, O or S), or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms (each independently N, O or S), R 1e is C 1-6 alkyl or C 1-6 hydroxyalkyl, R 2a and R 2b are each independently hydrogen, C 1-6 alkyl, halogen, C 1-6 haloalkyl, -CH2R 2c or NR 2a1 R 2b1 , each R 2a1 and R 2b1 are independently hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 hydroxyalkyl, C 2-6 alkoxyalkyl,1-6 Alkyl-NR 2a2 R 2b2 , C 3-10 Cycloalkyl or C 1-6 Alkyl-C 3-10 It is a cycloalkyl, Each R 2a2 and R 2b2 These are independently hydrogen or C 1-6 It is alkyl, Each R 2c NR is independent. 2a1 R 2b1 , a heterocycloalkyl ring with 1 to 4 heteroatoms (each independently N, O, or S), or a heteroaryl ring with 1 to 4 heteroatoms (each independently N, O, or S), wherein the heterocycloalkyl and heteroaryl rings each independently contain 0, 1, 2, 3, 4, or 5 R atoms. 2d It is substituted with the base, Each R 2d Independently, C 1-6 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 1-6 Hydroxyalkyl, C 2-6 Alkoxyalkyls, halogens, C 1-6 Haloalkyl, -OH, =O, =NH, -CN, -NO2, -C(O)H, -C(O)R 2e , -C(O)OR 2e -S(O)2R 2e , -C 1-6 Alkyl-(SO3 - ), -OP(=O)(OR 2e ) A heterocycloalkyl group of 3 to 10 members having 2,1 to 4 heteroatoms (each independently N, O, or S), or a heteroaryl group of 3 to 10 members having 1 to 4 heteroatoms (each independently N, O, or S), R 2e is C 1-6 Alkyl or C 1-6 It is a hydroxyalkyl, X is -N= or -C(R 3b )= and Each R 3a and R 3b These are, independently, hydrogen and C 1-6 Alkyl, halogen, C 1-6 Haloalkyl, CN, or -S(O)2R 3c And Each R 3c Independently, C 1-6 Alkyl, C 1-6 Haloalkyl, or C 6-12 It is an aryl, however each aryl independently has 0, 1, 2, 3, 4 or 5 C 1-6 Alkyl or C 1-6 It is substituted with a haloalkyl group.

[0061] The copolymer can be a random copolymer, an alternating copolymer, or a block copolymer. In some embodiments, the copolymer is a random copolymer.

[0062] The copolymer of the present invention may contain an additional repeating unit C, which is different from repeating units A and B. The copolymer of the present invention may contain an additional repeating unit D, which is different from repeating units A, B and C. The copolymer of the present invention may contain an additional repeating unit E, which is different from repeating units A, B, C and D. The copolymer of the present invention may contain an additional repeating unit F, which is different from repeating units A, B, C, D and E. Additional repeating units may be present in the copolymer of the present invention.

[0063] In some embodiments, the copolymer of the present invention is of formula J [A] x -[B] y -[C] z1 -[D] z2 -[E] z3 -[F] z4 (J) It is a copolymer having the following structure. In the formula, each repeating unit A, B, C, D, E, and F is independently either the structure of formula I or the structure of formula II, each A, B, C, D, E, and F is distinct, each subscript x and y is independently an integer between 1 and 1000, and each subscript z1, z2, z3, and z4 is independently an integer between 0 and 1000.

[0064] In some embodiments, the copolymer of the present invention is a copolymer of formula J, wherein A, B, C, D, E, and F are each independent repeating units having the structure of formula I.

[0065] In some embodiments, the copolymer of the present invention is of formula J-1 [A] x -[B] y -[C] z1 (J-1) (In the formula, A, B, and C are distinct, the subscripts x and y are independent integers between 1 and 1000, and the subscript z1 is independent integer between 0 and 1000.) It is a copolymer of formula J having the structure,

[0066] In some embodiments, the copolymer of the present invention is of formula J-2 [A] x -[B] y (J-2) (In the formula, A, B, and C are distinct, and the subscripts x and y are independent integers between 1 and 1000.) It is a copolymer of formula J or J-1 having the structure shown.

[0067] In some embodiments, the copolymer of the present invention is such that A is of formula Ia [ka] It is a copolymer of formula J, J-1, or J-2, which is a repeating unit having the structure shown.

[0068] In some embodiments, the copolymer of the present invention is such that each repeating unit of formula I is independently of formula Ia [ka] It is a copolymer of formula J, J-1, or J-2 having the structure shown.

[0069] In some embodiments, the copolymer of the present invention is each R 1c NR 1a1 R 1b1 or a 5 or 6-membered heterocycloalkyl ring having 1 or 2 heteroatoms (each independently N, O, or S) (wherein the heterocycloalkyl ring independently has 0 or 1 R 1d It is a copolymer of formula J, J-1, or J-2, which is substituted with a group.

[0070] In some embodiments, the copolymer of the present invention is each R 1c A heterocycloalkyl ring of 5 or 6 members having 1 or 2 heteroatoms (each independently N, O, or S) (where the heterocycloalkyl ring independently has 0 or 1 R 1d It is a copolymer of formula J, J-1, or J-2, which is substituted with a group. In some embodiments, the copolymer of the present invention is each R 1c The copolymer of formula J, J-1, or J-2 is a six-membered ring heterocycloalkyl having one or two heteroatoms (each independently N, O, or S). In some embodiments, the copolymer of the present invention has each R 1c However, each has 0 or 1 R independently 1d The copolymer of formula J, J-1, or J-2 is a morpholine, thiomorpholine, or piperazine substituted with a group. In some embodiments, the copolymer of the present invention is each R 1c It is a copolymer of formula J, J-1, or J-2, wherein is morpholine or thiomorpholine.

[0071] In some embodiments, the copolymers of the present invention have each R 1c independently being NR 1a1 R 1b1 and are copolymers of formula J, J-1 or J-2.

[0072] In some embodiments, the copolymers of the present invention have each R 1a1 and R 1b1 independently being hydrogen, C 1-6 alkyl, C 2-6 alkenyl or C 2-6 alkynyl and are copolymers of J, J-1 or J-2. In some embodiments, the copolymers of the present invention have each R 1a1 and R 1b1 independently being C 1-3 alkyl or C 2-4 alkenyl and are copolymers of formula J, J-1 or J-2. In some embodiments, the copolymers of the present invention have each R 1a1 and R 1b1 independently being methyl, ethyl or n-propyl and are copolymers of formula J, J-1 or J-2. In some embodiments, the copolymers of the present invention have each R 1a1 and R 1b1 independently being ethenyl, propenyl, n-butenyl, s-butenyl or isobutenyl and are copolymers of formula J, J-1 or J-2. In some embodiments, the copolymers of the present invention have each R 1a1 and R 1b1 independently being methyl or propenyl and are copolymers of formula J, J-1 or J-2. In some embodiments, the copolymers of the present invention have each R 1c independently being methylallylamine or diallylamine and are copolymers of formula J, J-1 or J-2.

[0073] In some embodiments, the copolymers of the present invention have each R 1d independently being C 1-6 alkyl, -C(O)R 1e -C(O)OR 1e -S(O)2R1e , -C 1-6 Alkyl-(SO3 - ) or -OP(=O)(OR 1e )2 is a copolymer of formula J, J-1, or J-2. In some embodiments, the copolymer of the present invention is each R 1d C 1-6 Alkyl, -S(O)2R 1e or -C 1-6 Alkyl-(SO3 - ) is a copolymer of formula J, J-1, or J-2. In some embodiments, the copolymer of the present invention is each R 1d -S(O)2R 1e It is a copolymer of formula J, J-1, or J-2.

[0074] In some embodiments, the copolymer of the present invention is R 1e C 1-6 It is an alkyl copolymer of formula J, J-1, or J-2. In some embodiments, the copolymer of the present invention is R 1e C 1-3 It is an alkyl copolymer of formula J, J-1, or J-2. In some embodiments, the copolymer of the present invention is R 1e It is a copolymer of formula J, J-1, or J-2, wherein is methyl, ethyl, or n-propyl.

[0075] In some embodiments, the copolymer of the present invention is each R 1d -S(O)2-C 1-3 It is an alkyl copolymer of formula J, J-1, or J-2.

[0076] In some embodiments, the copolymer of the present invention is R 2a and R 2b It is a copolymer of formula J, J-1, or J-2, where each of the atoms is hydrogen.

[0077] In some embodiments, the copolymer of the present invention is R 3a It is a copolymer of formula J, J-1, or J-2, where -CN.

[0078] In some embodiments, the copolymer of the present invention is such that X is -C(R 3b )= is a copolymer of formula J, J-1, or J-2. In some embodiments, the copolymer of the present invention is R 3b It is a copolymer of formula J, J-1, or J-2, where -CN.

[0079] In some embodiments, the copolymer of the present invention has a structure in which A is [ka] PIM-13 having, or structure [ka] PIM-13S is a copolymer of formula J, J-1, or J-2 having [specific properties].

[0080] In some embodiments, the copolymer of the present invention has a structure in which A is [ka] PIM-13 is a copolymer of formula J, J-1, or J-2 having [the specified property].

[0081] In some embodiments, the copolymer of the present invention has B as PIM-1: [ka] It is a copolymer of formula J, J-1, or J-2.

[0082] In some embodiments, the copolymer of the present invention is B = SBC: [ka] It is a copolymer of formula J, J-1, or J-2.

[0083] In some embodiments, the copolymer of the present invention is B = PIM-MAA: [ka] It is a copolymer of formula J, J-1, or J-2.

[0084] In some embodiments, the copolymer of the present invention is B = PIM-DAA: [ka] It is a copolymer of formula J, J-1, or J-2.

[0085] In some embodiments, the copolymer of the present invention has a structure in which C [ka] It is a copolymer of formula J, J-1, or J-2, which is PzMeSO2 having [a specific compound].

[0086] In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where the subscript x is an integer between 10 and 500, the subscript y is an integer between 1 and 200, and each of the subscripts z1, z2, z3, and z4 is an integer between 0 and 100. In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where the subscript x is an integer between 10 and 300, the subscript y is an integer between 1 and 200, and each of the subscripts z1, z2, z3, and z4 is an integer between 0 and 100.

[0087] In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where each of the subscripts z1, z2, z3, and z4 is 0. In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where each of the subscripts z1, z2, z3, and z4 is an integer from 1 to 100.

[0088] The copolymer of the present invention can have a molar ratio of subscript x to subscript y of about 10:90 to about 99:1, or about 20:80 to about 98:2, about 25:75 to about 98:2, about 30:70 to about 97.5:2.5, about 50:50 to about 97.5:2.5, about 50:50 to about 95:5, or about 50:50 to about 90:10. The molar ratio of subscript x to other subscripts y is approximately 99:1, or approximately 98.5:1.5, 98:2, 97.5:2.5, 97:3, 96.5:3.5, 96:4, 95.5:4.5, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 87.5:12.5, 85:15, 82.5:17.5, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40:60, 35:65, 30:70, 25:75, 20:80, 15:85, 10:90, 5:95, or approximately 1:99. In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, wherein the molar ratio of subscript x to subscript y is about 10:90 to about 99:1.

[0089] The copolymer of the present invention has a weight-average molecular weight (M) of 1 kg / mol to 1000 kg / mol or 1 kDa to 1000 kDa. w Copolymers may have a weight-average molecular weight (M) of 10 kg / mol to 500 kg / mol, or 20 kg / mol to 400 kg / mol, or 30 kg / mol to 300 kg / mol, or 40 kg / mol to 200 kg / mol, or 50 kg / mol to 175 kg / mol, or 50 kg / mol to 150 kg / mol. w ) or number-average molecular weight. In some embodiments, the copolymer of the present invention has a weight-average molecular weight (M) of the copolymer. w The copolymer has a weight-average molecular weight (M) of the copolymer. In some embodiments, the copolymer of the present invention has a weight-average molecular weight (M) of the copolymer. w The copolymer has a weight-average molecular weight (M) of 10 kg / mol to 500 kg / mol. In some embodiments, the copolymer of the present invention has a weight-average molecular weight (M) of the copolymer. wThe copolymer has a weight-average molecular weight (M) of 35 kg / mol to 160 kg / mol. In some embodiments, the copolymer of the present invention has a weight-average molecular weight (M) of the copolymer. w The copolymer has a molecular weight of 55 kg / mol to 150 kg / mol. The molecular weight of the polymer can be calculated by various methods, including, but not limited to, size exclusion chromatography (SEC), laser light scattering, and MALDI-TOF. The molecular weight of the polymer in this invention is measured using a Waters APC SEC (size exclusion chromatography) system equipped with an RI detector for comparison with a polystyrene standard for relative molecular weight, or using a Malvern OMNISEC GPC equipped with a triple detector for absolute molecular weight measurement.

[0090] In some embodiments, the copolymer of the present invention has a weight-average molecular weight (M) of the copolymer. w The copolymer of formula J, J-1, or J-2 has a weight-average molecular weight (M) of the copolymer, with a molecular weight of 1 kg / mol to 1000 kg / mol. In some embodiments, the copolymer of the present invention has a weight-average molecular weight (M) of the copolymer. w The copolymer of formula J, J-1, or J-2 has a weight-average molecular weight (M) of the copolymer, with a molecular weight of 10 kg / mol to 500 kg / mol. In some embodiments, the copolymer of the present invention has a weight-average molecular weight (M) of the copolymer. w The copolymer of formula J, J-1, or J-2 has a weight-average molecular weight (M) of the copolymer, with a molecular weight of 35 kg / mol to 160 kg / mol. In some embodiments, the copolymer of the present invention has a weight-average molecular weight (M) of the copolymer. w The copolymer is of formula J, J-1, or J-2, with a concentration of 55 kg / mol to 150 kg / mol.

[0091] In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where A is PIM-13 and B is PIM-1. In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where A is PIM-13S and B is PIM-1. In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where A is PIM-13 and B is SBC.

[0092] In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where A is PIM-13 and B is PIM-MAA. In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, where A is PIM-13 and B is PIM-DAA.

[0093] In some embodiments, the copolymer of the present invention is a copolymer of formula J or J-1, where A is PIM-13, B is PIM-1, and C is PzMeSO2.

[0094] In some embodiments, the copolymer of the present invention has a structure [PIM-13] x -[PIM-1] y , [PIM-13S] x -[PIM-1] y , [PIM-13] x -[SBC] y , [PIM-13] x -[PIM-MAA] y , [PIM-13] x -[PIM-DAA] y ,or [PIM-13] x -[PIM-1] y -[PzMeSO2] z1 It is a copolymer of formula J, J-1, or J-2 having the following characteristics.

[0095] In some embodiments, the copolymer of the present invention has a structure [PIM-13] x -[PIM-1] y , [PIM-13S] x -[PIM-1] y , [PIM-13] x -[SBC] y ,or [PIM-13] x -[PIM-1] y -[PzMeSO2] z1 It is a copolymer of formula J, J-1, or J-2 having the following characteristics.

[0096] In some embodiments, the copolymer of the present invention has a structure [PIM-13] x -[PIM-1] y (In the formula, the subscript x ranges from approximately 30 to approximately 150, and the subscript y ranges from approximately 1 to approximately 120.) It is a copolymer of formula J, J-1, or J-2 having the following characteristics.

[0097] In some embodiments, the copolymer of the present invention has a structure [PIM-13S] x -[PIM-1] y (In the formula, the subscript x is approximately 50 to 200, and the subscript y is approximately 1 to 60.) It is a copolymer of formula J, J-1, or J-2 having the following characteristics.

[0098] In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, wherein the copolymer is a random copolymer having the following structure. a) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 97.5:2.5, and the weight-average molecular weight (M) of the random copolymer is w) is approximately 68 kg / mol. b) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 95:5, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 67 kg / mol. c) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 92.5:7.5, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 76 kg / mol. d) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 65 kg / mol. e) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 87.5:12.5, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 80 kg / mol. f) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 85:15, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 95 kg / mol. g) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 82.5:17.5, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 73 kg / mol. h) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 80:20, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 80 kg / mol. i) [PIM-13] x -[PIM-1] y In the equation, the ratio of the subscript x to the subscript y is approximately 70:30. j) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 10¹ kg / mol. k) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 30:70, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 78 kg / mol. l) [PIM-13S] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is... w The concentration is approximately 61 kg / mol. m) [PIM-13S] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 85:15, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 116 kg / mol. n) [PIM-13S] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 80:20, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 144 kg / mol. o) [PIM-13] x -[PIM-1] y-[PzMeSO2] z1 In the formula, the ratio of subscript x, subscript y, and subscript z1 is approximately 80:10:10, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 60 kg / mol. p) [PIM-13] x -[SBC] y In the formula, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 85 kg / mol. q) [PIM-13] x -[SBC] y In the formula, the ratio of subscript x to subscript y is approximately 70:30, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 156 kg / mol. r) [PIM-13] x -[SBC] y In the formula, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 99 kg / mol. s) [PIM-13] x -[PIM-MAA] y In the formula, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 95 kg / mol. t) [PIM-13] x -[PIM-DAA] y In the formula, the ratio of subscript x to subscript y is approximately 95:5, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 57 kg / mol. u) [PIM-13] x -[PIM-DAA] y In the formula, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is...w ) is approximately 63 kg / mol. v) [PIM-13] x -[PIM-DAA] y In the formula, the ratio of subscript x to subscript y is approximately 70:30, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 40 kg / mol. w) [PIM-13] x -[PIM-DAA] y In the formula, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is... w The concentration is approximately 61 kg / mol. x) [PIM-13] x -[PIM-DAA] y In the formula, the ratio of subscript x to subscript y is approximately 30:70, and the weight-average molecular weight (M) of the random copolymer is... w The concentration is approximately 56.6 kg / mol. y) [PIM-13] x -[PIM-DAA] y In the formula, the ratio of subscript x to subscript y is approximately 20:80, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 113 kg / mol. Or, z) [PIM-13] x -[PIM-DAA] y In the formula, the ratio of subscript x to subscript y is approximately 10:90, and the weight-average molecular weight (M) of the random copolymer is w The concentration is approximately 90.5 kg / mol.

[0099] In some embodiments, the copolymer of the present invention is a copolymer of formula J, J-1, or J-2, wherein the copolymer is a random copolymer having the following structure. a) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is 97.5:2.5, and the weight-average molecular weight (Mw) of the random copolymer is approximately 68 kg / mol. b) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 95:5, and the weight-average molecular weight (Mw) of the random copolymer is approximately 67 kg / mol. c) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 92.5:7.5, and the weight-average molecular weight (Mw) of the random copolymer is approximately 76 kg / mol. d) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (Mw) of the random copolymer is approximately 65 kg / mol. e) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 87.5:12.5, and the weight-average molecular weight (Mw) of the random copolymer is approximately 80 kg / mol. f) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 85:15, and the weight-average molecular weight (Mw) of the random copolymer is approximately 95 kg / mol. g) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 82.5:17.5, and the weight-average molecular weight (Mw) of the random copolymer is approximately 73 kg / mol. h) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 80:20, and the weight-average molecular weight (Mw) of the random copolymer is approximately 80 kg / mol. i) [PIM-13] x -[PIM-1] y In the equation, the ratio of the subscript x to the subscript y is approximately 70:30. j) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (Mw) of the random copolymer is approximately 10¹ kg / mol. k) [PIM-13] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 30:70, and the weight-average molecular weight (Mw) of the random copolymer is approximately 78 kg / mol. l) [PIM-13S] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (Mw) of the random copolymer is approximately 61 kg / mol. m) [PIM-13S] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 85:15, and the weight-average molecular weight (Mw) of the random copolymer is approximately 116 kg / mol. n) [PIM-13S] x -[PIM-1] y In the formula, the ratio of subscript x to subscript y is approximately 80:20, and the weight-average molecular weight (Mw) of the random copolymer is approximately 144 kg / mol. o) [PIM-13] x -[PIM-1] y -[PzMeSO2] z1 In the formula, the ratio of subscript x, subscript y, and subscript z1 is approximately 80:10:10, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 60 kg / mol. p) [PIM-13] x -[SBC] y In the formula, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 85 kg / mol. q) [PIM-13] x -[SBC] y In the formula, the ratio of subscript x to subscript y is approximately 70:30, and the weight-average molecular weight (M) of the random copolymer is... w ) is approximately 156 kg / mol. r) [PIM-13] x -[SBC] y In the formula, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is w ) is approximately 99 kg / mol.

[0100] The copolymers of the present invention can be prepared by various methods. For example, the spirobisindan and spirobischroman monomers can be condensed with tetrafluoroterephthalonitrile or other phthalonitriles using potassium carbonate or other suitable bases. Useful bases in preparing the copolymers include, but are not limited to, sodium carbonate, potassium carbonate, and cesium carbonate.

[0101] The copolymer of the present invention can be used as a film. In some embodiments, the present invention provides a film comprising the copolymer of the present invention. The copolymer film may contain various additional components.

[0102] III. Covered Separator In some embodiments, the present invention provides a coated separator comprising a porous membrane support and a membrane layer on the porous membrane support containing the copolymer of the present invention.

[0103] Figure 2A shows a coated separator 100 having a porous support 110 having a first surface 111 and a second opposite surface 112, and a copolymer layer 130.

[0104] The separator may contain the polymer of the present invention alone or in combination with other components. In some embodiments, the present invention is A porous support having a first surface and a second opposite surface, A first polymer layer, and Copolymer layer containing the copolymer of the present invention A multilayer coated separator comprising, The present invention provides a multilayer coated separator in which a first polymer layer is coated on a first surface of a porous support, and a copolymer layer is coated on top of the first polymer layer.

[0105] Figure 2B shows a multilayer coated separator 150 having a porous support 110 having a first surface 111 and a second opposite surface 112, a first polymer layer 120, and a copolymer layer 130.

[0106] porous support In some embodiments, the pore size of the porous support is about 0.01 micrometers to 5 micrometers, or more specifically about 0.02 micrometers to 0.5 micrometers. The porosity of the porous support may be about 20% to 85%, or more specifically about 30% to 60%. Those skilled in the art will understand that the pore size may be affected by the composition of the electrolyte supplied into the pores of the separator. For example, some components of the separator (e.g., the porous support or the first polymer layer) may swell and change their pore size when in contact with some material of the electrolyte. Unless otherwise specified, pore size and other similar parameters refer to the components of the separator before contact with the electrolyte.

[0107] Larger pore sizes allow for the use of a porous support much thicker than the first polymer layer without significantly impairing the overall permeability of the separator to the first species. In some embodiments, the thickness of the porous support is about 5 to 500 micrometers, or in certain embodiments, about 5 to 50 micrometers, or more specifically, about 10 to 30 micrometers. In the same or other embodiments, the thickness of the porous support may be about 1 to 50 times greater than the thickness of the first polymer layer, or more specifically, about 5 to 25 times greater.

[0108] Some examples of suitable materials for porous supports include poly(ethylene-co-tetrafluoroethylene (PETFE) and poly(ethylene chloro-co-trifluoroethylene) (e.g., fabrics woven from these, used alone or laminated with fluoropolymer microporous films), polyvinylidene difluoride, polytetrafluoroethylene (PTFE), polystyrene, polyaryl ethersulfone, polyvinyl chloride, polypropylene, polyethylene (including LDPE, LLDPE, HDPE, and ultra-high molecular weight polyethylene), polyamide, polyimide, polyacrylic, polyacetal, polycarbonate, polyester, polyetherimide, polyimide, polyketone, polyphenylene ether, polyphenylene sulfide, polymethylpentene, and polysulfone. Examples of porous supports include, but are not limited to, nonwoven glass, glass fiber materials, ceramics, metal oxides, organic and inorganic composites, and polypropylene films. Porous supports may also be supplied with additional coatings of a second suitable material, including, but not limited to, PTFV, PVDF, and PETFE. These examples of porous supports are manufactured under the name CELGARD® by Celanese Plastic Company, Inc. (Charlotte, North Carolina, USA), as well as by Asahi Kasei Corporation (Tokyo, Japan), Tonen Corporation (Tokyo, Japan), Ube Industries, Ltd. (Tokyo, Japan), Nitto Denko Corporation (Osaka, Japan), Nippon Kodo Paper Industries Co., Ltd. (Kochi, Japan), Entek (Lebanon, Oregon, USA), SK Innovation (Jongno-gu, South Korea), Sumitomo Corporation (Tokyo, Japan), Toray Industries, Inc. (Tokyo, Japan), and DuPont USA. It may or may not be available from Double Scope, Inc. (USA) (Wilmington, Delaware), Japan, and Parker Hannifin Filtration Group (Carson, California, USA).

[0109] In some embodiments, the multilayer coated separator is a separator in which the porous support comprises polyethylene, polypropylene, poly(tetrafluoroethylene) (PTFE), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), cellulose, ceramic, or a combination thereof. In some embodiments, the multilayer coated separator is a separator in which the porous support comprises polyethylene.

[0110] The porous support may have a thickness of approximately 3 to 200 micrometers, or approximately 5 to 100 micrometers, or approximately 10 to 50 micrometers, or approximately 9 to 25 micrometers, or approximately 10 to 20 micrometers, or more specifically approximately 15 to 30 micrometers. The porous support may have a thickness of approximately 5 micrometers, or approximately 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or approximately 20 micrometers.

[0111] First polymer layer The selective blocking properties of one or more polymer layers used in a separator stem from the composition of these layers or a specific pore structure. For the purposes of this disclosure, the term “blocking” is also referred to as screening, selection, or exclusion. In some embodiments, the pore structure of the polymer layers appears as a network of interconnected pores having small pore size, a narrow pore size distribution, a high surface area, and high porosity, as further described below. In some embodiments, the pore structure of the polymer layers appears as an array of channels having small pore size, a narrow pore size distribution, a high surface area, and high porosity, as further described below. In addition to these blocking properties, the first polymer layers have a variety of other properties that make them suitable for electrochemical cell applications, such as chemical and electrochemical stability, wettability, thickness, and thermal stability.

[0112] The blocking mechanism is based on chemical exclusion (non-wettability) or size exclusion effects occurring on a nanometer to sub-nanometer scale (winding ion penetration pathways are established within the polymer layer). For example, the polymer layer may allow Li ions (or other similar species described below) to pass through while blocking larger electrolytes such as solvents. The membrane may be formed from a ladder polymer having angled spirocenters and no rotatable bonds in the polymer backbone, or bonds in the backbone where the rotation of the bonds is restricted. These features provide an inefficient solid dense packing with a porosity of about 10% to 40% of the bulk powder, or more specifically about 20% to 30%. The pores may then be filled with inorganic components to leave a non-porous or partially porous polymer layer.

[0113] The first polymer layer may contain any suitable polymer. In some embodiments, the multilayer coated separator is a separator in which the first polymer layer is substantially insoluble in the carbonate electrolyte. Typical carbonate electrolytes are described herein. For example, the first polymer layer may be more than 50% insoluble in the carbonate electrolyte, or more than 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or more than 99% insoluble in the carbonate electrolyte.

[0114] In some embodiments, the multilayer coated separator is a separator in which the first polymer layer is substantially insoluble in an electrolyte containing one or more lithium salts. Typical electrolytes containing one or more lithium salts are described herein. For example, the first polymer layer may be more than 50% insoluble in an electrolyte containing one or more lithium salts, or more than 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or more than 99% insoluble in an electrolyte containing one or more lithium salts.

[0115] The first polymer layer may include one or more different polymer layers. For example, the first polymer layer may include the first polymer layer, the second polymer layer, or more polymer layers. In some embodiments, the multilayer coated separator is a separator in which the first polymer layer comprises polyacrylonitrile, poly(acrylonitrile-methyl acrylate), poly(acrylonitrile-co-methacrylic acid), poly(acrylonitrile-acrylic acid), poly(acrylonitrile-itaconic acid), poly(acrylonitrile-methyl methacrylate), poly(acrylonitrile-itaconic acid-methyl acrylate), poly(acrylonitrile-methacrylic acid-methyl acrylate), poly(acrylonitrile-vinylpyridine), poly(acrylonitrile-vinyl chloride), poly(acrylonitrile-vinyl acetate), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), a second intrinsically microporous polymer different from the first intrinsically microporous polymer, or a combination thereof. In some embodiments, the multilayer coated separator is a separator in which the first polymer layer comprises poly(acrylonitrile-co-methyl acrylate), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), a second intrinsically microporous polymer different from the first intrinsically microporous polymer, or a combination thereof.

[0116] PIM polymer layer Examples of intrinsically microporous polymers useful for the electrochemical devices of the present invention include those described in U.S. Patent No. 10,710,065 and U.S. Patent No. 11,394,082, U.S. Patent Publication No. 2021 / 0309802 and U.S. Patent Publication No. 2019 / 0326578 (each of which is incorporated herein by reference in whole). In some embodiments, the copolymer layer is the copolymer of the present invention.

[0117] High free volume and microporosity are required to achieve the extremely high ion transport necessary for fast charging and high-power applications. Polymers exhibiting these properties are so-called high free volume polymers. These high-permeability polymers have been primarily applied to gas separation. Some examples include certain substituted polyacetylenes (e.g., PTMSP), certain perfluoropolymers (e.g., Teflon® AF), certain poly(norbornene), intrinsically microporous polymers, and certain polyimides. Their microporosity has been demonstrated by molecular modeling and positron lifetime spectroscopy (PALS). High-permeability polyacetylenes have bulky side chain groups that suppress conformational changes and force the backbone into a twisted shape. These rigid polymer polymers cannot be properly densely packed in the solid state, resulting in high free volume. The free volume distribution includes cleaved elements, such as in glassy polymers, and continuous fine voids. In Teflon® perfluoropolymers, their high free volume, coupled with a high barrier to rotation between adjacent dioxolane rings, leads to low packing density and therefore high permeability due to the weak interchain interactions well-known in fluoropolymers. In the case of poly(norvolene) and PTMSPs, the presence of bulky trimethylsilyl groups on the ring significantly limits the degree of freedom of the polymer to undergo steric changes. In inherently microporous polymers (PIMs), molecular linkers containing twist points are held in a non-coplanar orientation by rigid molecules, preventing the resulting polymer from being close-packed and ensuring high microporosity. The concept of PIMs has been reported for polyimides [PM Budd and NB McKeown, “Highly permeable polymers for gas separation membranes,” Polymer Chemistry, 1, 63-68, 2010].

[0118] PIMs are classified into two distinct types: i) non-network (linear) polymers, which may be soluble in organic solvents, and ii) network polymers, which are generally insoluble, although this also depends on the choice of monomers. PIMs possess an internal molecular free volume (IMFV), which is a measure of concavity and is defined by Swager as the difference in volume of concave units compared to non-concave shapes [TM Long and TM Swager, “Minimization of Free Volume: Alignment of Triptycenes in Liquid Crystals and Stretched Polymers”, Adv. Mater, 13, 8, 601-604, 2001]. While the intrinsic microporosity in linear PIMs is argued to derive from impermeable concavities given by their twisted structure, in network PIMs, the microporosity is also argued to derive from concavities associated with macrorings. In non-network PIMs, rotation of single bonds must be avoided, but branching and crosslinking in network PIMs are thought to avoid structural rearrangement that may result in a loss of microporosity (McKeown, 2010), and therefore single bonds can exist without a loss of microporosity. In general, network PIMs have been observed to have greater microporosity than non-network PIMs due to their macrocyclization [NB McKeown, PM Budd, “Exploitation of Intrinsic Microporosity in Polymer-Based Materials”, Macromolecules, 43, 5163-5176, 2010]. However, conventional network PIMs are not soluble and can only be incorporated into membranes when mixed as a filler with soluble PIMs or other microporous soluble materials containing soluble polymers. In non-network PIMs, there is a strict requirement that there should be no single bonds in the polymer backbone in order to prevent rotational freedom and provide intrinsic microporosity. This requires a highly rigid and twisted molecular structure, resulting in a difficult-to-handle polymer shape that cannot be efficiently packed tightly in space.Molecules with unwieldy shapes are those that cause packing problems due to their concave surfaces. However, concave-shaped molecules are not sufficient because, in order to give non-network PIMs microporosity, the voids must be sufficiently interconnected so that transport occurs with minimal energy (i.e., intrinsic microporosity) [NB McKeown, PM Budd, “Exploitation of Intrinsic Microporosity in Polymer-Based Materials”, Macromolecules, 43, 5163-5176, 2010]. Non-network PIMs may be soluble and therefore suitable for use in casting films by phase inversion or for coating support films to create thin-film composites. However, their solubility in various solvents limits their application to organic solvent nanofiltration [Ulbricht M, Advanced functional polymer membranes, Single Chain Polymers, 47, 2217-2262, 2006].

[0119] U.S. Patent No. 7,690,514 (B2) describes an intrinsically microporous material comprising an organic polymer consisting of a first generally planar species linked by linkers having a twist point, such that two adjacent first planar species linked by linkers are held in a non-coplanar orientation. Preferred twist points are spiro groups, bridged ring portions and sterically crowded bonds around them in which rotation is restricted. Since these non-network PIMs may be soluble in common organic solvents, it is possible to cast them into films or coat them over other support films to produce thin-film composites.

[0120] PIM-1 (soluble PIM) membranes exhibit gas permeability exceeding only very high free volume polymers such as Teflon® AF2400 and PTMSP, and show selectivity exceeding Robeson's 1991 upper limit for gas pairs such as CO2 / CH4 and O2 / N2. Studies have shown that permeability is improved by methanol treatment, which helps wash out residual casting solvent and allows for chain relaxation [PM Budd and NB McKeown, D Fritsch, “Polymers of Intrinsic Microporosity (PIMs): High free volume Polymers for membrane applications”, Macromol Symp, 245-246, 403-405, 2006].

[0121] Various polyimides with properties similar to microporous polymers (PIMs) were prepared by Ghanem et al., and membrane gas permeation experiments showed that these PIM-polyimides were the most permeable of all polyimides and had near-upper selectivity for several important gas pairs [BG Ghanem, NB McKeown, PM Budd, NM Al-Harbi, D Fritsch, K Heinrich, L Starannikova, A Tokarev and Y Yampolskii, “Synthesis, characterization, and gas permeation properties of a novel group of polymers with intrinsic microporosity: PIM-polyimides”, Macromolecules, 42, 7781–7888, 2009].

[0122] U.S. Patent No. 7,410,525 (B1) describes a polymer / polymer mixed matrix membrane containing a soluble, intrinsically microporous polymer as a microporous packing material for use in gas separation applications.

[0123] International Publication No. 2005 / 113121 (PCT / GB2005 / 002028) describes the formation of thin-film composite materials from PIM by coating a PIM organic solvent solution onto a support film and then, optionally, crosslinking the PIM film to enhance its stability in organic solvents.

[0124] To improve the stability of soluble PIM membranes, U.S. Patent No. 7,758,751 (B1) describes high-performance UV crosslinked membranes from intrinsically microporous polymers (PIMs), as well as their use in gas separation, liquid separation including organic solvents such as olefins / paraffins, deep desulfurization of gasoline and diesel fuels, and ethanol / water separation.

[0125] In some embodiments, the copolymer layer comprises a polymer having chains of repeating units bonded to one another. Each unit may include a first substantially planar species that contains at least one aromatic ring and also includes a rigid linker having a spiro group, a bridged ring moiety, or a twisted portion which is a sterically crowded single covalent bond. The rigid linker restricts the rotation of the first planar species in a non-coplanar orientation. In some embodiments, at least 50 mol% (or 70%, 80%, or even 90%) of the first planar species in the chain are connected by rigid linkers to up to two other planar species so as not to have a crosslinked covalent three-dimensional structure. Thus, the polymer may include rigid linkers having twisted portions. Since these polymer chains are not densely packed together due to their rigid twisted structure, the copolymer layer has inherent microporosity and possibly nanoporosity. Thus, this combination of non-dense-packed and non-crosslinked polymer chains extends in the three-dimensional direction. It may also be considered a non-network polymer. Cross-linked polymers are also within the range.

[0126] In some embodiments, the surface area of ​​the PIM polymer layer before filling with inorganic components (measured by nitrogen adsorption of the dry powder before film treatment or by related techniques) is at least 200 m². 2 / g or at least 500m 2 / g, for example 200m 2 / g~2200m 2 / g, or more specifically 600m 2 / g~900m 2 It may also be / g. A typical method for measuring surface area is nitrogen adsorption BET. Surface area is directly related to porosity and is essential for efficient transport of the supporting electrolyte between electrodes and for the operation of higher-power cells. Typical porosity is in the range of 20% to 70%, or more specifically, 30% to 60%. The surface area of ​​the PIM polymer layer is 100m² 2 / g, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, or 3000m 2 The concentration can be 100 m / g to 3000 m / g, for example. In some embodiments, the multilayer coated separator has a copolymer layer that is measured by nitrogen adsorption BET and is 100 m 2 / g~3000m 2 This is a separator with a surface area of ​​ / g.

[0127] In some embodiments, the multilayer coated separator is a separator in which the average pore size of the copolymer layer before the inorganic component is filled is less than 100 nm, or about 0.1 nm to about 20 nm, or about 0.1 nm to about 10 nm, or about 0.1 nm to about 5 nm, or about 0.1 nm to about 2 nm, or about 0.1 nm to about 1 nm. For example, the average pore size of the copolymer layer can be less than about 10 nm, or about 9, 8, 7, 6, 5, 4, 3, 2, or 1 nm. For example, the average pore size of the copolymer layer can be about 10 nm, or about 9, 8, 7, 6, 5, 4, 3, 2, or 1 nm. This pore size ensures that some substances (e.g., substances with a unit size larger than the pore size) are blocked by the copolymer layer, while other substances (e.g., substances with a smaller unit size) are allowed to pass through. In some embodiments, the multilayer coated separator is a separator in which the copolymer layer has an average pore size of 0.1 nm to 10 nm. In some embodiments, the multilayer coated separator is a separator in which the copolymer layer has an average pore size of 0.1 nm to 2 nm. In some embodiments, the multilayer coated separator is a separator in which the copolymer layer has an average pore size of 0.1 nm to 1 nm.

[0128] In some embodiments, the multilayer coated separator has a number-average molecular weight (M) of the copolymer layer. n ) is 1 × 10 3 ~2000×10 3 kg / mol, or more specifically 15 × 10⁻⁶ 3 ~500×10 3 kg / mol, or 20 × 10 3 ~200×10 3 The separator has a molecular weight of kg / mol. Polymers with a larger number-average molecular weight contribute to enhancing the mechanical properties of the formed film.

[0129] The copolymer layer can be a film cast, sprayed, or coated from a solution (e.g., onto a porous support), a composite material composed of multiple individual film layers, a self-supporting film, or a film supported (e.g., by a porous support).

[0130] In some embodiments, the multilayer coated separator is a separator in which the copolymer layer has a thickness of about 5 nanometers to 20 micrometers, or about 100 nanometers to 10 micrometers, or more specifically about 500 nanometers to 5 micrometers.

[0131] The microporosity of the polymer layer was measured using nitrogen adsorption measurement (BET calculation) and its high surface area (approximately 680-850 m²) 2 This is demonstrated by / g). The presence of cyano and methyl groups is optional; they may be omitted or substituted with other simple substituents. Each phenyl group may contain one or more substituents. Furthermore, the nature and arrangement of substituents on the spiro-indan moiety may be chosen to provide any desired configuration around the carbon atom common to both five-membered rings.

[0132] IV. Electrolytes The electrochemical cell of the present invention also includes an electrolyte, such as a carbonate-based electrolyte. The electrolyte can have various components, such as alkyl carbonates, fluorinated carbonates, diisocyanates, lithium salts, or combinations thereof. The present invention also includes an electrolyte having alkyl carbonates, fluorinated carbonates, diisocyanates, and lithium salts.

[0133] In some embodiments, the present invention provides an electrolyte comprising an alkyl carbonate, a fluorinated carbonate, a diisocyanate, and a first lithium salt. In some embodiments, the electrolyte comprises a second lithium salt different from the first lithium salt.

[0134] In some embodiments, the electrolyte includes a carbonate electrolyte. The carbonate electrolyte is given by the formula R′-OC(O)OR″ (wherein R′ and R″ are each independently C 1-6 Alkyl, C 2-6 Alkenil, C 1-6 Haloalkyl, C 3-6 Cycloalkyl or C 6-12The carbonate electrolyte may have the formula R′-OC(O)OR″ (wherein R′ and R″ are each independently C 1-6 Alkyl, C 2-6 Alkenyl, or C 1-6 The carbonate electrolyte may have the formula R′-OC(O)OR″ (wherein R′ and R″ are each independently C 1-3 Alkyl or C 1-4 The carbonate electrolyte may have the formula R′-OC(O)OR″ (wherein R′ and R″ are each independently C 1-6 It is alkyl.) It can be an alkyl carbonate. Carbonate electrolytes are given by formula R′-OC(O)OR″ (where R′ is C 1-6 Alkyl or C 1-6 It is a haloalkyl, and R'' is C 1-6 It can be a fluorinated carbonate of a haloalkyl group, where each haloalkyl group is a fluoroalkyl group, or where R′ and R″ can be combined to form a 5-6 membered heterocycloalkyl group that can be substituted with 0, 1, 2, 3, 4, or 5 fluorine atoms.

[0135] Typical alkyl carbonates used as electrolytes include, but are not limited to, the following. [Table 1]

[0136] In some embodiments, the alkyl carbonate is dimethyl carbonate.

[0137] Typical fluorinated carbonates of electrolytes include, but are not limited to, fluoroethylene carbonate, CH3OC(O)OCH2CF3, CH3OC(O)OCH2CF2CHF2, CH3OC(O)OCH2CF2CHF2, CF3CH2OC(O)OCH2CF3, CH3OC(O)OCH2CF2CF2CF3, CH3CH2OC(O)OCH2CF2CF3, CH3CH2OC(O)OCH2CF2CHF2, or CH3OC(O)OCH2CF2CF2CF3.

[0138] Typical electrolyte diisocyanates include, but are not limited to, torylene-2,4-diisocyanate or torylene-2,6-diisocyanate.

[0139] The lithium salt in the electrolyte composition of the present invention can be any suitable lithium salt. For example, suitable lithium salts include, but are not limited to, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or combinations thereof. In some embodiments, the lithium salt can be lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or combinations thereof.

[0140] In some embodiments, the electrolyte composition is an electrolyte composition in which the first lithium salt comprises lithium bis(fluorosulfonyl)imide (LiFSi), lithium hexafluorophosphate, or a combination thereof.

[0141] The first lithium salt can be present in the electrolyte composition in any suitable amount. For example, the first lithium salt can be present in the electrolyte composition in amounts of 0.1-20 mol%, 0.1-20 mol%, 1-20 mol%, 5-20 mol%, 5-15 mol%, 8-12 mol%, or 9-11 mol%. Typical amounts of the first lithium salt in the electrolyte composition of the present invention include, but are not limited to, about 5 mol%, or about 6, 7, 8, 9, 10, 11, 12, 13, 14, or about 15 mol%.

[0142] The electrolyte composition of the present invention may contain one or more lithium salts. For example, the electrolyte composition may contain one, two, three, four, or more different lithium salts as defined above. In some embodiments, the electrolyte composition is an electrolyte composition comprising a single lithium salt. In some embodiments, the electrolyte composition is an electrolyte composition comprising two different lithium salts. In some embodiments, the electrolyte composition is an electrolyte composition comprising three different lithium salts.

[0143] The electrolyte composition of the present invention may also include a second lithium salt different from the first lithium salt. In some embodiments, the electrolyte composition is an electrolyte composition comprising a second lithium salt different from the first lithium salt.

[0144] In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt comprises lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, lithium bis(trifluoromethanesulfonyl)imide, lithium difluorophosphate, lithium nitrate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, or a combination thereof. In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt comprises lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium, lithium difluoro(oxalato)borate, or a combination thereof. In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt comprises lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium. In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt comprises lithium difluoro(oxalato)borate. In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt comprises lithium nitrate.

[0145] The second lithium salt can be present in the electrolyte composition in any suitable amount. For example, the second lithium salt can be present in the electrolyte composition in amounts of 0.1-10 mol%, 0.1-5 mol%, 0.5-5 mol%, 0.5-4 mol%, 0.5-3.5 mol%, 1-3 mol%, 1.0-2.5 mol%, or 1.5-2.5 mol%. Typical amounts of the second lithium salt in the electrolyte composition of the present invention include, but are not limited to, about 1.5 mol%, or about 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or about 2.5 mol%.

[0146] In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt is present in an amount of 0.1 to 5 mol%. In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt is present in an amount of 0.5 to 3.5 mol%. In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt is present in an amount of 1 to 3 mol%. In some embodiments, the electrolyte composition is an electrolyte composition in which the second lithium salt is present in an amount of 1.5 to 2.5 mol%.

[0147] In some embodiments, the present invention is Dimethyl carbonate in amounts of 25-75 mol%, Fluoroethylene carbonate in amounts of 20-65 mol%, 0.1 to 10 mol% of trilene-2,6-diisocyanate, Lithium bis(fluorosulfonyl)imide in amounts of 1-20 mol%, and 0.1 to 10 mol% of lithium difluoro(oxalato) borate It provides electrolytes containing [specific components].

[0148] In some embodiments, the present invention is Approximately 48 mol% of dimethyl carbonate, Approximately 39 mol% of fluoroethylene carbonate, Approximately 1 mol% of trilene-2,6-diisocyanate, Approximately 10 mol% of lithium bis(fluorosulfonyl)imide, and Approximately 2 mol% of lithium difluoro(oxalato) borate It provides electrolytes including [specific electrolytes].

[0149] V. Electrochemical cell In some embodiments, the present invention provides an electrochemical cell comprising an anode, a cathode, a separator of the present invention, and an electrolyte.

[0150] In some embodiments, the electrochemical device is an electrochemical cell. In some embodiments, the electrochemical cell includes a positive electrode, a negative electrode, a separator, and an electrolyte.

[0151] In some embodiments, the present invention provides an electrochemical cell comprising an anode, a cathode, a coated separator of the present invention, and an electrolyte. Figure 3A shows an electrochemical cell 200 having an anode 210, a cathode 220, and a coated separator 100. The separator 100 is positioned between the anode 210 and the cathode 220. The separator provides electronic insulation between the anode and the cathode. At least a portion of the electrolyte is positioned within the separator.

[0152] In some embodiments, the present invention provides an electrochemical cell comprising an anode, a cathode, a multilayer coated separator of the present invention, and an electrolyte. Figure 3B shows an electrochemical cell 200 having an anode 210, a cathode 220, and a multilayer coated separator 150. The separator 100 is positioned between the anode 210 and the cathode 220. The separator provides electronic insulation between the anode and the cathode. At least a portion of the electrolyte is positioned within the separator.

[0153] In some embodiments, the electrochemical cell is an electrochemical cell in which a multilayer coated separator is located between the anode and the cathode. In some embodiments, the electrochemical cell is an electrochemical cell in which the multilayer coated separator is oriented such that a first surface of the support material faces toward the anode.

[0154] In some embodiments, the electrochemical cell of the present invention is an electrochemical cell in which the electrolyte is the electrolyte of the present invention. In some embodiments, the electrolyte may include one or more lithium salts. In some embodiments, the electrolyte may be a carbonate electrolyte.

[0155] In some embodiments, the electrochemical cell of the present invention is an electrochemical cell in which the electrolyte comprises a first lithium salt. In some embodiments, the electrochemical cell of the present invention is an electrochemical cell in which the electrolyte comprises a second lithium salt different from the first lithium salt.

[0156] In some embodiments, the electrochemical cell of the present invention is an electrochemical cell in which the electrolyte comprises lithium bis(fluorosulfonyl)imide, lithium difluoro(oxalato)borate, or lithium hexafluorophosphate.

[0157] In some embodiments, the electrochemical cell of the present invention is an electrochemical cell in which the electrolyte is E1, E2, LP40, LP57, LP57.2, or LP71.

[0158] In some embodiments, the electrochemical cell of the present invention has an electrolyte, Dimethyl carbonate in amounts of 25-75 mol%, Fluoroethylene carbonate in amounts of 20-65 mol%, 0.1 to 10 mol% of trilene-2,6-diisocyanate, Lithium bis(fluorosulfonyl)imide in amounts of 1-20 mol%, and 0.1 to 10 mol% of lithium difluoro(oxalato) borate It is an electrochemical cell that includes [a specific component].

[0159] In some embodiments, the electrochemical cell of the present invention has an electrolyte, Approximately 48 mol% of dimethyl carbonate, Approximately 39 mol% of fluoroethylene carbonate, Approximately 1 mol% of trilene-2,6-diisocyanate, Approximately 10 mol% of lithium bis(fluorosulfonyl)imide, and Approximately 2 mol% of lithium difluoro(oxalato) borate It is an electrochemical cell that includes [a specific component].

[0160] In some embodiments, the electrochemical device is a lithium-ion battery having a carbon-based anode, a metal anode or a semimetallic anode and a metal oxide cathode or conversion cathode. [Examples]

[0161] VI. Examples The following ingredients were used. [Table 2]

[0162] Additional molecular weight measurements are performed using a Waters APC SEC (size exclusion chromatograph) system with an RI detector to measure relative MW compared to a polystyrene standard, or using a Malvern OMNISEC GPC with a triple detector to measure absolute MW.

[0163] Molecular weight information for PIM-13 and copolymers was measured using a Waters Acquity advanced polymer chromatography system equipped with a refractive index detector, with chloroform as the mobile phase. Relative molecular weights were determined using calibration curves generated from polystyrene standards ranging from 0.266 to 1760 kg / mol.

[0164] A. Intermediate Intermediate 1: SBI-thiomorpholine(1) [ka] Paraformaldehyde (4.41 g, 147 mmol, 2.5 equivalents), thiomorpholine (14.71 mL, 147 mmol, 2.5 equivalents), and ethanol (300 mL) were added to a 1 L two-necked round-bottom flask equipped with a reflux condenser. The reaction mixture was purged with argon for 25 minutes, and then heated under reflux for 1 hour. After heating for 1 hour, 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindan (20 g, 58.8 mmol, 1 equivalent) was added, and the reaction mixture was stirred under reflux under argon for 24 hours, at which point a white precipitate was observed. The reaction mixture was then cooled to room temperature, poured into heptane (700 mL), and cooled to 0°C. Next, the reaction mixture was filtered, washed with heptane (2 × 50 mL), and dried under vacuum to obtain SBI-morpholine (5.23 g, yield 15.6%). 1 H-NMR(400MHz,DMSO-d6,δ):δ 10.98(s,2H),8.36(s,2H),6.52(s,2H),3.09(dd,4H),2.52(m,16H),2.15(dd,4H),1.30(s,6H),1.20(s,6H).

[0165] Intermediate 2: SBI-piperidine-MeSO2(2) [ka] Paraformaldehyde (1.10 g, 36.7 mmol, 2.5 equivalents), piperidine methyl sulfate (6.03 g, 36.7 mmol, 2.5 equivalents), and ethanol (75 mL) were added to a 250 L two-necked round-bottom flask equipped with a reflux condenser. The reaction mixture was purged with argon for 25 minutes and then heated under reflux for 1 hour. After heating for 1 hour, 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindan (5 g, 14.7 mmol, 1 equivalent) was added, and the reaction mixture was stirred under reflux under argon for 24 hours, at which point a white precipitate was observed. Next, the reaction mixture was cooled to room temperature, the solvent was removed by rotary evaporation, and the resulting solid was purified using a silica column chromatography with a mobile phase of ethyl acetate and hexane. The mixture was then dried under vacuum to obtain SBI-piperidine-MeSO2 (1.29 g, yield 12.6%). 1 H-NMR(400MHz,DMSO-d6,δ):δ 10.52(2H,s),8.31(2H,s),6.53(2H,s),3.12(12H,m),2.25(12H,m),1.32(6H,s),1.18(6H,s).

[0166] B. Copolymer Example 1: PIM-13 / 1(97.5 / 2.5)(3) [ka] In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.772 g, 1.433 mmol, 0.956 equivalents), SBI (0.013 g, 0.037 mmol, 0.025 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1 (97.5 / 2.5) (0.775 g, 81%, M w A solution of 67.8 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.03H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0167] Example 2: PIM-13 / 1(95 / 5)(4) In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.752 g, 1.397 mmol, 0.931 equivalents), SBI (0.025 g, 0.074 mmol, 0.049 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1(95 / 5)(0.848g, 89.2%, M wA solution of 66.9 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.05H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0168] Example 3: PIM-13 / 1(92.5 / 7.5)(5) In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.733 g, 1.360 mmol, 0.907 equivalents), SBI (0.038 g, 0.110 mmol, 0.074 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1 (92.5 / 7.5) (0.807 g, 85.5%, M w A solution of 76.0 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.07H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0169] Example 4: PIM-13 / 1(90 / 10)(6) In a dry 500 mL two-necked round-bottom flask equipped with a vacuum adapter and septum, tetrafluoroterephthalonitrile (2.106 g, 10.52 mmol, 1 equivalent), SBI-morpholine (5.00 g, 9.28 mmol, 0.882 equivalents), SBI (0.351 g, 1.03 mmol, 0.098 equivalents), and anhydrous DMF (110 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (5.93 g, 42.94 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (300 mL), filtered, and washed with additional water (100 mL) and ethanol (200 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1(90 / 10)(5.86g, 88.9%, M w A solution of 64.8 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.13H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0170] Example 5: PIM-13 / 1(87.5 / 12.5)(7) In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.693 g, 1.286 mmol, 0.858 equivalents), SBI (0.063 g, 0.184 mmol, 0.122 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1 (87.5 / 12.5) (0.783 g, 84.3%, Mw A solution of 79.5 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.12H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0171] Example 6: PIM-13 / 1(85 / 15)(8) In a dried 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.673 g, 1.250 mmol, 0.833 equivalents), SBI (0.075 g, 0.221 mmol, 0.147 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1(85 / 15)(0.785g, 85.1%, M w A solution of 95.0 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.14H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0172] Example 7: PIM-13 / 1(82.5 / 17.5)(9) In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.653 g, 1.213 mmol, 0.809 equivalents), SBI (0.088 g, 0.257 mmol, 0.172 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1 (82.5 / 17.5) (0.809 g, 88.4%, M w A solution of 73.0 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.16H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0173] Example 8: PIM-13 / 1(80 / 20)(10) In a dry 500 mL two-neck round-bottom flask equipped with a vacuum adapter and septum, tetrafluoroterephthalonitrile (2.104 g, 10.52 mmol, 1 equivalent), SBI-morpholine (4.44 g, 8.245 mmol, 0.784 equivalents), SBI (0.702 g, 2.061 mmol, 0.196 equivalents), and anhydrous DMF (110 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (5.93 g, 42.94 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (300 mL), filtered, and washed with additional water (100 mL) and ethanol (200 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1(80 / 20)(5.86g, 88.9%, Mw A solution of 79.6 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.2H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0174] Example 9: PIM-13 / 1(70 / 30)(11) In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.554 g, 1.029 mmol, 0.686 equivalents), SBI (0.150 g, 0.441 mmol, 0.294 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid was dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1(70 / 30)(701 mg, 79.6%) as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.31H,s),3.54(4H,s),2.99(3H,m),2.24(5H,m),1.36(6H,d).

[0175] Example 10: PIM-13 / 1(50 / 50)(12) In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.396 g, 0.735 mmol, 0.490 equivalents), SBI (0.250 g, 0.735 mmol, 0.490 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid was dried, stirred with 25 mg / mL of methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1(50 / 50) (0.699 g, 85%, Mw=101 kg / mol) as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.80(1H,s),6.43(0.48H,s),1.87(3.54H,s),2.99(1.44H,m),2.28(3.17H,s),1.35(6H,d).

[0176] Example 11: PIM-13 / 1(30 / 70)(13) In a dried 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.238 g, 0.441 mmol, 0.294 equivalents), SBI (0.350 g, 1.029 mmol, 0.686 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred with 25 mg / mL of 1,4-dioxane for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1(30 / 70)(0.650g, 85%, M wA solution of 78.2 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.80(1H,s),6.43(0.48H,s),1.87(3.54H,s),2.99(1.44H,m),2.28(3.17H,s),1.35(6H,d).

[0177] Example 12: PIM-13S / 1(90 / 10)(14) [ka] In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-thiomorpholine (753 mg, 1.32 mmol, 0.88 equivalents), SBI (51 mg, 0.150 mmol, 0.10 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13S / 1(90 / 10)(826 mg, 84.1%, M w A solution of 61.1 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.82(1H,s),6.44(0.09H,s),2.7(10H,m),1.35(6H,d).

[0178] Example 13: PIM-13S / 1(85 / 15)(15) In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-thiomorpholine (713 mg, 1.25 mmol, 0.83 equivalents), SBI (75.0 mg, 0.220 mmol, 0.15 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13S / 1(85 / 15)(656 mg, 67.9%, M w (=116 kg / mol) was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.82(1H,s),6.44(0.12H,s),2.7(10H,m),1.35(6H,d).

[0179] Example 14: PIM-13S / 1(80 / 20)(16) In a dried 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-thiomorpholine (671 mg, 1.18 mmol, 0.78 equivalents), SBI (102 mg, 0.300 mmol, 0.20 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dried potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13S / 1(80 / 20)(696g, 73.3%, M w (=144 kg / mol) was obtained as a bright yellow solid. 1H-NMR(400MHz,CDCl3,δ):δ 6.82(1H,s),6.44(0.16H,s),2.7(10H,m),1.35(6H,d).

[0180] Example 15: PIM-13 / 1 / PzMeSO2(80 / 10 / 10)(17) [ka] In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (633 mg, 1.18 mmol, 0.78 equivalents), SBI (50 mg, 0.15 mmol, 0.10 equivalents), SBI-piperidine-MeSO2 (102 mg, 0.15 mmol, 0.1 equivalent), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / 1 / PzMeSO2(80 / 10 / 10)(0.805g, 84%, M w A solution of 59.8 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(1H,s),6.44(0.1H,s),3.54(2.95H,s),3.00(3.13H,m),2.24(4.45H,s),1.36(6H,d).

[0181] Example 16: PIM-13 / SBC(90 / 10): [ka] In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.712 g, 1.322 mmol, 0.882 equivalents), 6,6′,7,7′-tetrahydroxy-4,4,4′,4′-tetramethyl-2,2′-spirovichroman (0.055 g, 0.147 mmol, 0.098 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / SBC(90 / 10)(0.84g, 89%, M w A solution of 84.9 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.97(0.11H,s),6.81(1H,s),6.33(0.11H,s),3.54(4H,s),3.08(3H,m),2.25(5H,m),2.03(0.22H,d),1.59(0.66H,d),1.36(6H,d).

[0182] Example 17: PIM-13 / SBC(70 / 30): In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.554 g, 1.029 mmol, 0.686 equivalents), 6,6′,7,7′-tetrahydroxy-4,4,4′,4′-tetramethyl-2,2′-spirovichroman (0.164 g, 0.441 mmol, 0.294 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / SBC(70 / 30)(0.74g, 83%, M w (=156 kg / mol) was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.97(0.44H,s),6.81(1H,s),6.33(0.44H,s),3.54(4H,s),3.08(3H,m),2.25(5H,m),2.03(0.88H,d),1.59(2.64H,d),1.36(6H,d).

[0183] Example 18: PIM-13 / SBC(50 / 50): In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-morpholine (0.396 g, 0.735 mmol, 0.490 equivalents), 6,6′,7,7′-tetrahydroxy-4,4,4′,4′-tetramethyl-2,2′-spirovichroman (0.274 g, 0.735 mmol, 0.490 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / SBC(50 / 50)(0.74g, 87%, M w A solution of 99.3 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.97(1H,s),6.81(1H,s),6.33(1H,s),3.54(4H,s),3.08(3H,m),2.25(5H,m),2.03(2H,d),1.59(6H,d),1.36(6H,d).

[0184] Example 19: PIM-13 / MAA(50 / 50)(22): [ka] In a 250 mL two-necked round-bottom flask equipped with a vacuum adapter and septum, tetrafluoroterephthalonitrile (3 g, 15 mmol, 1 equivalent), SBI-methylallylamine (3 g, 3.724 g, 7.35 mmol, 0.49 equivalents), SBI-morpholine (3.959 g, 7.35 mmol, 0.49 equivalents), and anhydrous DMAc (135 mL) were added. The reaction mixture was then heated to 120 °C, and anhydrous potassium carbonate (8.46 g, 61.2 g, 4.08 equivalents) was added. The reaction mixture was stirred under nitrogen at 120 °C for 2 hours, then precipitated in water (500 mL), vacuum filtered, washed with additional water (250 mL) and ethanol (250 mL), and dried under vacuum. This crude product is further purified by stirring the crude solid with 60 / 40 (vol / vol) methyl ethyl ketone and ethanol at a concentration of 25 mg / mL for 24 hours, followed by filtration, to obtain a bright yellow solid PIM-13 / MAA(50 / 50) (8.86 g, 94%, M) w We obtained a value of 95.0 kg / mol. 1 H-NMR(400MHz,CDCl3,δ):δ 6.79(1H,s),5.59(0.5H,s),5.00(1H,d),2.99(9H,m),1.85(1.5H,s),1.34(6H,d).

[0185] Example 20: PIM-13 / DAA(95 / 5): [ka] In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-DAA (18 mg, 41 mg, 0.074 mmol, 0.049 equivalents), SBI-morpholine (752 mg, 1.397 mmol, 0.931 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred in 25 mg / mL methyl ethyl ketone for 24 hours to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / DAA(95 / 5)(0.97g, ~100%, M w A solution of 56.7 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(2H,s),5.51(0.09H,s),4.98(0.26H,d),3.25(14.96H,m),2.24(9.12H,s),1.40(6H,s),1.32(6H,s).

[0186] Example 21: PIM-13 / DAA(90 / 10): In a 250 mL two-necked round-bottom flask equipped with a vacuum adapter and septum, tetrafluoroterephthalonitrile (3 g, 15 mmol, 1 equivalent), SBI-DAA (18 g, 0.820 g, 1.47 mmol, 0.098 equivalents), SBI-morpholine (7.13 g, 13.23 mmol, 0.882 equivalents), and anhydrous DMF (160 mL) were added. The reaction mixture was then heated to 65 °C, and anhydrous potassium carbonate (8.46 g, 61.2 g, 4.08 equivalents) was added. The reaction mixture was stirred under nitrogen at 65 °C for 2 hours, then precipitated in water (500 mL), vacuum filtered, washed with additional water (250 mL) and ethanol (250 mL), and dried under vacuum. This crude product is further purified by stirring the crude solid with methyl ethyl ketone at a concentration of 25 mg / mL for 24 hours and filtering, obtaining a bright yellow solid PIM-13 / DAA(90 / 10) (7.43 g, 67.5%, M w We obtained a value of 63.2 kg / mol. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(2H,s),5.51(0.27H,s),4.98(0.61H,d),3.25(13.6H,m),2.24(8.59H,s),1.40(6H,s),1.32(6H,s).

[0187] Example 22: PIM-13 / DAA(70 / 30): In a dry 20 mL scintillation vial, tetrafluoroterephthalonitrile (0.300 g, 1.50 mmol, 1 equivalent), SBI-DAA (18, 249 mg, 0.446 mmol, 0.297 equivalents), SBI-morpholine (560 mg, 1.404 mmol, 0.693 equivalents), and anhydrous DMF (16 mL) were added. The reaction mixture was heated to 65 °C, dry potassium carbonate (0.846 g, 6.12 mmol, 4.08 equivalents) was added, and the mixture was stirred overnight under argon. The reaction mixture was then cooled to room temperature, precipitated in water (100 mL), filtered, and washed with additional water (50 mL) and ethanol (100 mL). Next, this solid is dried, stirred for 24 hours with 1:1 (vol / vol) methyl ethyl ketone / ethanol at 25 mg / mL to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / DAA(70 / 30) (0.963g, ~94%, M w A solution of 39.6 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.81(2H,s),5.51(1.06H,s),4.98(2.15H,d),3.25(13.7H,m),2.24(7.51H,s),1.40(6H,s),1.32(6H,s).

[0188] Example 23: PIM-13 / DAA(50 / 50): In a 100 mL two-necked round-bottom flask equipped with a vacuum adapter and septum, tetrafluoroterephthalonitrile (0.600 g, 3 mmol, 1 equivalent), SBI-DAA (18, 0.830 g, 1.486 mmol, 0.495 equivalents), SBI-morpholine (0.800 g, 1.486 mmol, 0.495 equivalents), and anhydrous DMAc (27 mL) were added. The reaction mixture was then heated to 120 °C, and anhydrous potassium carbonate (1.692 g, 12.24, 4.08 equivalents) was added. The reaction mixture was stirred under nitrogen at 120 °C for 2 hours, then precipitated in water (200 mL), vacuum filtered, washed with additional water (100 mL) and ethanol (100 mL), and dried under vacuum. Next, this solid is dried, stirred for 24 hours with 60 / 40 (vol / vol) methyl ethyl ketone / ethanol at 25 mg / mL to remove oligomeric impurities, filtered, and dried under vacuum to obtain PIM-13 / DAA(50 / 50) (1.07 g, 55%, M w A solution of 61.0 kg / mol was obtained as a bright yellow solid. 1 H-NMR(400MHz,CDCl3,δ):δ 6.83(2H,s),5.51(1.90H,s),4.98(3.41H,d),3.25(12.51H,m),2.24(7.10H,s),1.38(6H,s),1.32(6H,s).

[0189] Example 24: PIM-13 / DAA(30 / 70): In a 250 mL two-necked round-bottom flask equipped with a vacuum adapter and septum, tetrafluoroterephthalonitrile (3 g, 15 mmol, 1 equivalent), SBI-DAA (18 g, 5.984 g, 10.71 mmol, 0.714 equivalents), SBI-morpholine (2.473 g, 4.59 mmol, 0.306 equivalents), and anhydrous DMF (160 mL) were added. The reaction mixture was then heated to 65 °C, and anhydrous potassium carbonate (8.46 g, 61.2 mmol, 4.08 equivalents) was added. The reaction mixture was stirred overnight under nitrogen at 65 °C, then precipitated in water (500 mL), vacuum filtered, washed with additional water (250 mL) and ethanol (250 mL), and dried under vacuum. This crude product is further purified by stirring the crude solid with 60 / 40 (vol / vol) methyl ethyl ketone and ethanol at a concentration of 25 mg / mL for 24 hours, followed by filtration, to obtain a bright yellow solid PIM-13 / DAA(30 / 70) (8.18 g, 81%, M w We obtained a value of 56.6 kg / mol. 1 H-NMR(400MHz,CDCl3,δ):δ 6.83(2H,s),5.51(2.70H,s),5.01(5.28H,d),3.11(13.52H,m),2.22(4.12H,s),1.39(6H,s),1.33(6H,s).

[0190] Example 25: PIM-13 / DAA(20 / 80): In a 250 mL two-necked round-bottom flask equipped with a vacuum adapter and septum, tetrafluoroterephthalonitrile (3 g, 15 mmol, 1 equivalent), SBI-DAA (18 g, 6.839 g, 12.24 mmol, 0.816 equivalents), SBI-morpholine (1.648 g, 3.06 mmol, 0.204 equivalents), and anhydrous DMF (160 mL) were added. The reaction mixture was then heated to 65 °C, and anhydrous potassium carbonate (8.46 g, 61.2 g, 4.08 equivalents) was added. The reaction mixture was stirred under nitrogen at 65 °C for 2 hours, then precipitated in water (500 mL), vacuum filtered, washed with additional water (250 mL) and ethanol (250 mL), and dried under vacuum. This crude product is further purified by stirring the crude solid with 60 / 40 (vol / vol) methyl ethyl ketone and ethanol at a concentration of 25 mg / mL for 24 hours, followed by filtration, to obtain a bright yellow solid PIM-13 / DAA(20 / 80) (8.07 g, 80%, M) w We obtained a result of 113 kg / mol. 1 H-NMR(400MHz,CDCl3,δ):δ 6.83(2H,s),5.51(3.18H,s),4.98(6.24H,d),3.25(13.72H,m),2.24(3.43H,s),1.38(6H,s),1.33(6H,s).

[0191] Example 26: PIM-13 / DAA(10 / 90): In a 250 mL two-necked round-bottom flask equipped with a vacuum adapter and septum, tetrafluoroterephthalonitrile (3 g, 15 mmol, 1 equivalent), SBI-DAA (18, 7.694 g, 13.77 mmol, 0.918 equivalents), SBI-morpholine (0.824 g, 1.53 mmol, 0.102 equivalents), and anhydrous DMF (160 mL) were added. The reaction mixture was then heated to 65 °C, and anhydrous potassium carbonate (8.46 g, 61.2, 4.08 equivalents) was added. The reaction mixture was stirred under nitrogen at 65 °C for 2 hours, then precipitated in water (500 mL), vacuum filtered, washed with additional water (250 mL) and ethanol (250 mL), and dried under vacuum. This crude product is further purified by stirring the crude solid with 60 / 40 (vol / vol) methyl ethyl ketone and ethanol at a concentration of 25 mg / mL for 24 hours, followed by filtration, to obtain a bright yellow solid PIM-13 / DAA(10 / 90) (8.26 g, 81%, M w We obtained a value of 90.5 kg / mol. 1 H-NMR(400MHz,CDCl3,δ):δ 6.83(2H,s),5.51(3.72H,s),4.98(7.13H,d),3.25(13.97H,m),2.24(2.77H,s),1.38(6H,s),1.33(6H,s).

[0192] C. Dissolution Examples Example 1: Study of dissolution in lithium-ion electrolytes Electrolyte preparation E1: Dimethyl carbonate:fluoroethylene carbonate (50:48 wt / wt) and 1.2 mol / kg lithium bis(fluorosulfonyl)imide and 0.2 mol / kg lithium (difluorooxalatovolate) in 2 wt% trilen-2,6-diisocyanate.

[0193] E2: 1,2-Dimethoxyethane:1H,1H,5H-Octafluoropentyl 1,1,2,2-Tetrafluoroethyl ether (OFE):1,1,2,2-Tetrafluoroethyl 2,2,2,3-Tetrafluoropropyl ether (TTE) (44:28:27 wt / wt / wt) and 3.0 mol / kg of lithium bis(fluorosulfonyl)imide and 0.2 mol / kg of lithium (difluorooxalatovolate) in 2 wt% ethoxy(pentafluoro)triphosphatidine.

[0194] LP40: 1.0 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate:diethyl carbonate (1:1 wt / wt)

[0195] LP57: 1.0 M LiPF6 in ethylene carbonate:ethylmethyl carbonate (3:7 wt / wt)

[0196] LP57.2: 1.0 M LiPF6 in ethylene carbonate:ethylmethyl carbonate (3:7 wt / wt) containing 2 wt% vinylene carbonate.

[0197] LP71: 1.0 M LiPF6 in ethylene carbonate:diethyl carbonate:dimethyl carbonate (1:1:1 wt / wt / wt)

[0198] Research on dissolution in lithium-ion electrolytes: In a dilute liquid electrolyte lithium-ion battery cell design with a 1 μm coating layer across the entire surface of the battery separator and an electrolyte-to-cathode nominal capacity ratio of approximately 2 g / Ah, the ratio of polymer material to total liquid electrolyte content is approximately 14 mg polymer / mL lithium-ion electrolyte. Therefore, to measure the intrinsic solubility of various homopolymer and copolymer formulations in lithium-ion battery electrolytes, 14 mg / mL mixtures of each polymer were prepared in a representative lithium-ion battery electrolyte (E1). The solutions were vigorously stirred for 24 hours, filtered by syringe to remove undissolved polymer fractions, and then diluted six-fold with additional E1 for spectroscopic analysis. The total content of dissolved polymer in each sample was measured by UV-Vis spectroscopy. Table 1 shows copolymers exhibiting decreased solubility compared to PIM-13, indicating complete solubility in E1 at this concentration. By adjusting the PIM-1 monomer content, copolymer solubility can be reduced to undetectable concentrations. [Table 3]

[0199] Research on high-dilution dissolution in lithium-ion electrolytes: 1 g / m 2 Polyethylene battery separators coated with copolymer at a film weight were punched out to a diameter of 14 mm and immersed in an excess volume (1 mL) of E1, E2, or LP57 electrolyte for 24 hours. The solution was then observed for evidence of polymer dissolution, indicated by the yellow color of the solution. The results were classified into three categories. Nearly complete dissolution of the coating (A) A yellow color is observed in the electrolyte solution, but the coating remains intact (B). No discoloration of the solution (C) [Table 4]

[0200] Although the above invention is described in some detail by examples and embodiments for clarity, those skilled in the art will understand that modifications and alterations may be made within the scope of the appended claims. Furthermore, each reference provided herein is incorporated by reference in whole to the same extent as if each reference were incorporated by reference individually. In the event of any conflict between this application and the references provided herein, this application shall prevail.

Claims

1. A copolymer comprising multiple repeating units A and B, A and B are independent of each other, Equation I 【Chemistry 1】 Structure or formula II 【Chemistry 2】 It is a repeating unit having the structure, A and B are different, R １ａ and R １ｂ These are, independently, hydrogen and C １－６ Alkyl, halogen, C １－６ Haloalkyl, -CH ２ R １ｃ or NR １ａ１ R １ｂ１ And, Each R １ａ１ and R １ｂ１ is, independently, hydrogen, C １－６ alkyl, C ２－６ alkenyl, C ２－６ alkynyl, C １－６ hydroxyalkyl, C ２－６ alkoxyalkyl, C １－６ alkyl-NR １ａ２ R １ｂ２ , C ３－１０ cycloalkyl or C １－６ alkyl-C ３－１０ cycloalkyl, and Each R １ａ２ and R １ｂ２ These are independently hydrogen or C １－６ It is alkyl, Each R １ｃ NR is independent. １ａ１ R １ｂ１ , a heterocycloalkyl ring of 5 to 10 members having 1 to 4 heteroatoms (each independently N, O, or S), or a heteroaryl ring of 5 to 10 members having 1 to 4 heteroatoms (each independently N, O, or S), wherein the heterocycloalkyl and heteroaryl each independently have 0, 1, 2, 3, 4, or 5 R １ｄ It is substituted with the base, Each R １ｄ Independently, C １－６ Alkyl, C ２－６ Alkenil, C ２－６ Alkinyl, C １－６ Hydroxyalkyl, C ２－６ Alkoxyalkyls, halogens, C １－６ Haloalkyl, -OH, =O, =NH, -CN, -NO ２ , -C(O)H, -C(O)R １ｅ , -C(O)OR １ｅ , -S(O) ２ R １ｅ , -C １－６ Alkyl-(SO ３ － ), -OP(=O)(OR １ｅ ) ２ , a heterocycloalkyl group of 3 to 10 members having 1 to 4 heteroatoms (each independently N, O, or S), or a heteroaryl group of 3 to 10 members having 1 to 4 heteroatoms (each independently N, O, or S), R １ｅ is C １－６ Alkyl or C １－６ It is a hydroxyalkyl, R ２ａ and R ２ｂ These are, independently, hydrogen and C １－６ Alkyl, halogen, C １－６ Haloalkyl, -CH ２ R ２ｃ or NR ２ａ１ R ２ｂ１ And, Each R ２ａ１ and R ２ｂ１ These are, independently, hydrogen and C １－６ Alkyl, C ２－６ Alkenil, C ２－６ Alkinyl, C １－６ Hydroxyalkyl, C ２－６ Alkoxyalkyl, C １－６ Alkyl-NR ２ａ２ R ２ｂ２ , C ３－１０ Cycloalkyl or C １－６ Alkyl-C ３－１０ It is a cycloalkyl, Each R ２ａ２ and R ２ｂ２ These are independently hydrogen or C １－６ It is alkyl, Each R ２ｃ NR is independent. ２ａ１ R ２ｂ１ , a 5-10 membered heterocycloalkyl ring having 1-4 heteroatoms (each independently N, O, or S), or a 5-10 membered heteroaryl ring having 1-4 heteroatoms (each independently N, O, or S), wherein the heterocycloalkyl and heteroaryl rings each independently have 0, 1, 2, 3, 4, or 5 R ２ｄ It is substituted with the base, Each R ２ｄ is independently C １－６ alkyl, C ２－６ alkenyl, C ２－６ alkynyl, C １－６ hydroxyalkyl, C ２－６ alkoxyalkyl, halogen, C １－６ haloalkyl, -OH, =O, =NH, -CN, -NO ２ , -C(O)H, -C(O)R ２ｅ , -C(O)OR ２ｅ , -S(O) ２ R ２ｅ , -C １－６ alkyl-(SO ３ － ), -OP(=O)(OR ２ｅ ), ２ a 3- to 10-membered heterocycloalkyl having 1 to 4 heteroatoms (each independently N, O or S), or a 3- to 10-membered heteroaryl having 1 to 4 heteroatoms (each independently N, O or S), R ２ｅ is C １－６ Alkyl or C １－６ It is a hydroxyalkyl, X is -N= or -C(R ３ｂ )=, Each R ３ａ and R ３ｂ These are, independently, hydrogen and C １－６ Alkyl, halogen, C １－６ Haloalkyl, -CN, or -S(O) ２ R ３ｃ And Each R ３ｃ Independently, C １－６ Alkyl, C １－６ Haloalkyl or C ６－１２ It is an aryl group, where each aryl group independently has 0, 1, 2, 3, 4, or 5 bases (each independently has C １－６ Alkyl or C １－６ A copolymer substituted with a haloalkyl group.

2. The copolymer according to claim 1, wherein the copolymer is a random copolymer.

3. Formula J [A] ｘ -[B] ｙ -[C] ｚ１ -[D] ｚ２ -[E] ｚ３ -[F] ｚ４ (J) A copolymer according to claim 1 or 2 having the structure, The repeating units A, B, C, D, E, and F each independently have the structure of formula I or formula II, and A, B, C, D, E, and F are all different. The subscripts x and y are each independent integers between 1 and 1000. The subscripts z1, z2, z3, and z4 are each independent integers between 0 and 1000, forming a copolymer.

4. The copolymer according to claim 3, wherein A, B, C, D, E, and F are each independently repeating units having the structure of formula I.

5. Formula J-1 [A] ｘ -[B] ｙ -[C] ｚ１ (J-1) A copolymer according to claim 3 or 4 having the structure, A, B, and C are all different. The subscripts x and y are each independent integers between 1 and 1000. The subscript z1 is an independent integer between 0 and 1000, forming a copolymer.

6. Formula J-2 [A] ｘ -[B] ｙ (J-2) A copolymer according to any one of claims 3 to 5 having the structure, A and B are different, A copolymer in which the subscripts x and y are each independent integers between 1 and 1000.

7. A is equation Ia 【Transformation 3】 The copolymer according to claim 1 or 6, which is a repeating unit having the structure.

8. Each repeating unit of equation I is independent of equation Ia 【Chemistry 4】 A copolymer according to claim 1 or 6, having the structure described above.

9. Each R １ｃ However, it became independent, NR １ａ１ R １ｂ１ , or a 5 or 6-membered heterocycloalkyl ring having 1 or 2 heteroatoms (each independently N, O, or S), wherein the heterocycloalkyl ring independently has 0 or 1 R １ｄ A copolymer according to any one of claims 1 to 8, which is substituted with a group.

10. Each R １ｃ The copolymer according to any one of claims 1 to 9, wherein each is a six-membered ring heterocycloalkyl having one or two heteroatoms (each independently N, O, or S).

11. Each R １ａ１ and R １ｂ１ C １－３ Alkyl or C ２－４ The copolymer according to any one of claims 1 to 9, wherein the copolymer is an alkenyl.

12. Each R １ｄ -S(O) ２ -C １－３ The copolymer according to claim 1 or 9, wherein it is alkyl.

13. R ２ａ and R ２ｂ The copolymer according to any one of claims 1 to 12, wherein each of them is hydrogen.

14. R ３ａ The copolymer according to any one of claims 1 to 13, wherein is -CN.

15. X is -C(R ３ｂ The copolymer according to any one of claims 1 to 14, wherein ) =

16. R ３ｂ The copolymer according to any one of claims 1 to 15, wherein is -CN.

17. A is structure 【Transformation 5】 PIM-13 having, or structure 【Transformation 6】 The copolymer according to any one of claims 1 to 16, which is PIM-13S having the following properties.

18. B is PIM-1: 【Transformation 7】 The copolymer according to any one of claims 1 to 17.

19. B is SBC: 【Transformation 8】 The copolymer according to any one of claims 1 to 17.

20. B is PIM-MAA: 【Chemistry 9】 The copolymer according to any one of claims 1 to 17.

21. B is PIM-DAA: 【Chemistry 10】 The copolymer according to any one of claims 1 to 17.

22. C is structure 【Chemistry 11】 PzMeSO ２ The copolymer according to any one of claims 3 to 18.

23. The subscript x is an integer between 10 and 500. The subscript y is an integer between 1 and 200. The subscripts z1, z2, z3, and z4 are each independent integers between 0 and 100. The copolymer according to any one of claims 3 to 22.

24. The subscript x is an integer between 10 and 300. The subscript y is an integer between 1 and 200. The subscripts z1, z2, z3, and z4 are each independent integers between 0 and 100. The copolymer according to any one of claims 3 to 23.

25. The copolymer according to any one of claims 3 to 24, wherein the subscripts z1, z2, z3, and z4 are each 0.

26. The copolymer according to any one of claims 3 to 24, wherein the subscripts z1, z2, z3, and z4 are each independently integers from 1 to 100.

27. The copolymer according to any one of claims 1 to 26, wherein the molar ratio of subscript x to subscript y is about 10:90 to about 99:

1.

28. Weight-average molecular weight (M) of copolymer ｗ The copolymer according to any one of claims 1 to 27, wherein the concentration is 1 kg / mol to 1000 kg / mol.

29. Weight-average molecular weight (M) of copolymer ｗ The copolymer according to any one of claims 1 to 28, wherein the concentration is 10 kg / mol to 500 kg / mol.

30. Weight-average molecular weight (M) of copolymer ｗ The copolymer according to any one of claims 1 to 29, wherein the concentration is 35 kg / mol to 160 kg / mol.

31. structure [PIM-13] ｘ -[PIM-1] ｙ 、 [PIM-13S] ｘ -[PIM-1] ｙ 、 [PIM-13] ｘ - [SBC] ｙ ,or [PIM-13] ｘ -[PIM-1] ｙ -[PzMeSO ２ ] ｚ１ The copolymer according to any one of claims 17 to 30, having the following characteristics.

32. structure [PIM-13] ｘ -[PIM-1] ｙ (In the formula, the subscript x ranges from approximately 30 to approximately 150, and the subscript y ranges from approximately 1 to approximately 120.) The copolymer according to any one of claims 17 to 31.

33. structure [PIM-13S] ｘ -[PIM-1] ｙ (In the formula, the subscript x ranges from approximately 50 to approximately 200, and the subscript y ranges from approximately 1 to approximately 60.) The copolymer according to any one of claims 17 to 31.

34. Copolymer, structure a) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 97.5:2.5, and the weight-average molecular weight (M) of the random copolymer. ｗ ) is approximately 68 kg / mol. b) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 95:5, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 67 kg / mol. c) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 92.5:7.5, and the weight-average molecular weight (M) of the random copolymer. ｗ ) is approximately 76 kg / mol. d) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 65 kg / mol. e) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 87.5:12.5, and the weight-average molecular weight (M) of the random copolymer. ｗ ) is approximately 80 kg / mol. f) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 85:15, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 95 kg / mol. g) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 82.5:17.5, and the weight-average molecular weight (M) of the random copolymer. ｗ ) is approximately 73 kg / mol. h) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 80:20, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 80 kg / mol. i) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 70:30.) j) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 101 kg / mol. k) [PIM-13] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 30:70, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 78 kg / mol. l) [PIM-13S] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 61 kg / mol. m) [PIM-13S] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 85:15, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 116 kg / mol. n) [PIM-13S] ｘ - [PIM-1] ｙ (However, the ratio of subscript x to subscript y is approximately 80:20, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 144 kg / mol. o) [PIM-13] ｘ - [PIM-1] ｙ - [PzMeSO ２ ] ｚ１ (However, the ratio of subscript x, subscript y, and subscript z1 is approximately 80:10:10, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 60 kg / mol. p) [PIM-13] ｘ - [SBC] ｙ (However, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 85 kg / mol. q) [PIM-13] ｘ - [SBC] ｙ (However, the ratio of subscript x to subscript y is approximately 70:30, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 156 kg / mol. r) [PIM-13] ｘ - [SBC] ｙ (However, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 99 kg / mol. s) [PIM-13] ｘ - [PIM-MAA] ｙ (However, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 95 kg / mol. t) [PIM-13] ｘ - [PIM-DAA] ｙ (However, the ratio of subscript x to subscript y is approximately 95:5, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 57 kg / mol. u) [PIM-13] ｘ - [PIM-DAA] ｙ (However, the ratio of subscript x to subscript y is approximately 90:10, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 63 kg / mol. v) [PIM-13] ｘ - [PIM-DAA] ｙ (However, the ratio of subscript x to subscript y is approximately 70:30, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 40 kg / mol. w) [PIM-13] ｘ - [PIM-DAA] ｙ (However, the ratio of subscript x to subscript y is approximately 50:50, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 61 kg / mol. x) [PIM-13] ｘ - [PIM-DAA] ｙ (However, the ratio of subscript x to subscript y is approximately 30:70, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 56.6 kg / mol. y) [PIM-13] ｘ - [PIM-DAA] ｙ (However, the ratio of subscript x to subscript y is approximately 20:80, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 113 kg / mol. z) [PIM-13] ｘ - [PIM-DAA] ｙ (However, the ratio of subscript x to subscript y is approximately 10:90, and the weight-average molecular weight (M) of the random copolymer is ｗ ) is approximately 90.5 kg / mol. The copolymer according to any one of claims 17 to 33, which is a random copolymer having the properties of the claim.

35. A coated separator comprising a porous membrane support and a membrane layer on the porous membrane support containing the copolymer according to any one of claims 1 to 34.

36. A-scatter, Cathode and, The separator described in claim 35, Electrolytes and An electrochemical cell containing [a specific component].

37. The electrochemical cell according to claim 36, wherein the electrolyte contains one or more lithium salts.

38. The electrochemical cell according to claim 36, wherein the electrolyte comprises a carbonate electrolyte.

39. The electrochemical cell according to claim 36, wherein the carbonate electrolyte is E1, E2, LP40, LP57, LP57.2, or LP71.

40. Electrolytes, Dimethyl carbonate in amounts of 25-75 mol%, Fluoroethylene carbonate in amounts of 20-65 mol%, 0.1 to 10 mol% of trilene-2,6-diisocyanate, Lithium bis(fluorosulfonyl)imide in amounts of 1 to 20 mol%, and 0.1 to 10 mol% of lithium difluoro(oxalato) borate An electrochemical cell according to any one of claims 36 to 38, including the following:

41. Electrolytes, Approximately 48 mol% of dimethyl carbonate, Approximately 39 mol% of fluoroethylene carbonate, Approximately 1 mol% of trilene-2,6-diisocyanate, Approximately 10 mol% of lithium bis(fluorosulfonyl)imide, and Approximately 2 mol% of lithium difluoro(oxalato) borate An electrochemical cell according to any one of claims 36 to 40, including the following:

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