Single-ion conductive polymer and preparation method thereof

Abstract

The present technology relates to a method for producing a single ion conductive polymer comprising grafting a thiol-functionalized conductor compound onto a polymer compound to obtain a single ion conductive polymer. In certain embodiments, the thiol-functionalized conductor compound can be grafted to a polymer having a low Tg, which results in a single ion conductive polymer having improved conductivity.

Description

Technical Field

[0001] The present technology generally relates to single ion conducting polymer electrolytes, and in particular to single ion conducting polymers and methods of making the same. Background Art

[0002] Lithium batteries using lithium metal as negative electrodes have excellent energy density. However, in the case of repeated cycles, when the battery is recharged, such batteries may be affected by dendrite growth on the surface of the lithium metal electrode due to the uneven re-plating of lithium ions on the surface of the lithium metal electrode. In order to minimize the impact of the morphological evolution of the surface of the lithium metal anode (including dendrite growth), lithium metal batteries generally use solid polymer electrolytes and pressure systems suitable for resisting the pressure applied thereto, as described in U.S. Patent No. 6,007,935 (incorporated herein by reference). However, after multiple cycles, dendrites on the surface of the lithium metal anode may still grow to penetrate the solid polymer electrolyte and eventually cause a "soft" short circuit between the negative electrode and the positive electrode, resulting in decreased or poor battery performance. Therefore, the growth of dendrites deteriorates the cycle characteristics of the battery and constitutes a major limitation to the performance optimization of lithium batteries with metallic lithium anodes.

[0003] Since the late 1970s, various types of solid polymer electrolytes suitable for use with lithium metal electrodes have been developed to overcome this problem, but have been found to lack conductivity and / or mechanical properties. However, single-ion conducting polymer electrolytes (SIPEs) have emerged as promising candidates because the migration number of lithium cations is close to one and thus prevents the formation of concentration gradients across the electrolyte and, therefore, dendrite formation.

[0004] SIPEs are usually synthesized in two ways: (1) by synthesizing single-ion monomers and then polymerizing them, or (2) by post-functionalizing commercial polymers with single-ion conductor groups. The latter method is more cost-effective and has a wider range of polymer matrices to choose from for the synthesis of SIPEs. However, polymer post-functionalization usually requires efficient reactions to ensure high conversion rates. Examples of such synthetic routes include the synthesis of poly(ethylene oxide) methacrylate sulfonyl(trifluoromethylsulfonyl)imide lithium) (PEOMA-TFSI-Li+) monomers via copper-catalyzed alkyne-azide "click chemistry" cycloaddition, as shown in FIG1 (Li S. et al., ACS Energy Lett. 2018, 3, 1, 20-27, incorporated herein by reference (Li S. et al.)), or the use of polymers containing thiol groups, such as (mercaptopropyl)methylsiloxane homopolymer (PDMS-SH), as shown in FIG2, to graft TFSI monomers onto polymers (Zhao S. et al., ACS Appl. Energy Mater. 2020, 3, 12, 12540-12548, and Liang et al., Adv. Energy Mater. 2022, 2200013, both incorporated herein by reference).

[0005] "Click" reactions, such as the azide-alkyne click reaction demonstrated by Li S. et al., are generally considered to be a good choice for post-functionalization methods. However, such reactions involve the use of sodium azide, which is hazardous and difficult to handle in scale-up production. In addition, the alkyne groups required for this reaction are rarely present in commercial polymers; therefore, in such cases, additional reaction steps are required to modify the polymer and make it suitable for post-functionalization.

[0006] The inventors of the present technology have also recently discovered new methods for synthesizing LiTFSI monomers that reduce costs and have high atom economy (i.e., produce less reactant waste) compared to existing methods, especially due to the inclusion of a single step and bypassing the synthesis of nitrogen-based organic cation intermediates. These new synthetic routes can be applied to the preparation of SIPEs with styrene, acrylate or methacrylate backbones. However, the resulting homopolymers derived from such LiTFSI monomers have high glass transition temperatures (Tg) and low electrical conductivity at room temperature, which hinder their performance as electrolytes and ultimately hinder the performance of batteries.

[0007] Therefore, there is a need for alternative or improved SIPE synthesis methods that overcome or reduce at least some of the above-mentioned problems. Summary of the invention

[0008] In one aspect, a method for producing a single ion conducting polymer is provided, the method comprising grafting a thiol functionalized conductor compound onto a polymer compound to obtain a single ion conducting polymer. In certain embodiments, the thiol functionalized conductor compound can be grafted onto a polymer having a low Tg, which produces a single ion conducting polymer having improved conductivity.

[0009] In another aspect, a single ion conducting polymer having Formula A is provided:

[0010]

[0011] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; and

[0012] M + It is a monovalent cation.

[0013] In another aspect, a single ion conducting polymer having Formula B is provided:

[0014]

[0015] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0016] M + is a monovalent cation; and

[0017] Where 3≤n≤50.

[0018] In another aspect, a single ion conducting polymer having Formula C is provided:

[0019]

[0020] Where R f F; CF3; CF2CF3; (C2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0021] M + is a monovalent cation; and

[0022] Where 5≤n≤500.

[0023] In another aspect, a single ion conducting polymer having Formula D is provided:

[0024]

[0025] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0026] M + It is a monovalent cation;

[0027] 1≤m≤500;

[0028] 1≤n≤500; and

[0029] 2≤m+n≤1000.

[0030] In another aspect, a single ion conducting polymer having Formula E is provided:

[0031]

[0032] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0033] M + It is a monovalent cation;

[0034] 1≤m≤500;

[0035] 1≤n≤500;

[0036] 1≤l≤500, and

[0037] 3≤m+n+l≤1500.

[0038] In another aspect, a single ion conducting polymer having Formula F is provided:

[0039]

[0040] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0041] M + is a monovalent cation; and

[0042] 5≤n≤500.

[0043] In another aspect, a single ion conducting polymer having Formula G is provided:

[0044]

[0045] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0046] M + is a monovalent cation; and

[0047] 5≤n≤500.

[0048] In another aspect, a single ion conducting polymer having Formula H is provided:

[0049]

[0050] Wherein R is H or CH3;

[0051] 1≤m≤6000;

[0052] 0≤n≤1500;

[0053] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; and

[0054] M + It is a monovalent cation.

[0055] In another aspect, a single ion conducting polymer having Formula I is provided:

[0056]

[0057] Where Rf F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0058] M + It is a monovalent cation;

[0059] 10≤m≤3000; and

[0060] 50≤n≤6000.

[0061] In another aspect, a single ion conducting polymer having Formula J is provided:

[0062]

[0063] Where R is H, allyl,

[0064] or a combination thereof, and

[0065] At least one R is

[0066] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0067] M + is a monovalent cation; and

[0068] Where 100≤n≤6000.

[0069] In another aspect, a single ion conducting polymer having Formula K is provided:

[0070]

[0071] Wherein R is a linear C2-C6 alkyl group or a branched C3-C6 alkyl group,

[0072] R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0073] M + is a monovalent cation; and

[0074] 5≤n≤100.

[0075] In another aspect, a single ion conductive polymer electrolyte is provided, which includes the single ion conductive polymer of the present technology.

[0076] In another aspect, a solid-state battery is provided that includes a positive electrode, a negative electrode, and a single-ion conductive polymer electrolyte of the present technology.

[0077] In another aspect, methods of the present technology include grafting a thiol-functionalized conductor compound onto a polymer compound via a thiol-ene "click" reaction.

[0078] On the other hand, the methods of the present technology do not require a heating step.

[0079] On the other hand, the method of the present technology is scalable and secure.

[0080] On the other hand, the methods of the present technology require alkenyl groups, which are widely available in commercial polymers or can be obtained by simple modification of commercial polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0081] Reference will now be made to the drawings.

[0082] Figure 1 shows the existing synthetic route of poly(ethylene oxide) methacrylate sulfonyl(trifluoromethylsulfonyl)imide lithium) (PEOMA-TFSI-Li+) using azide-alkyne click chemistry according to Li S. et al., ACS Energy Lett. 2018, 3, 1, 20-27 (incorporated herein by reference).

[0083] FIG. 2 shows an existing synthesis route of PDMS-based SIPE using PDMS-SH as the starting material according to Zhao S. et al., ACS Appl. Energy Mater. 2020, 3, 12, 12540-12548 (incorporated herein by reference).

[0084] Figure 3 A graph showing a thiol-functionalized conductor compound (lower graph) of one embodiment used in a method according to the present technology compared to a LiTFSI-acrylate compound (upper graph) and 1,3-propanedithiol (middle graph) as starting materials used to synthesize the thiol-functionalized conductor compound. 1 H-NMR spectrum.

[0085] Figure 4 Shows Figure 3 Thiol-functionalized conductor compounds 1 H-NMR integration, where mono-substitution of the dithiol is evident by: (1) a 1:1 ratio of peak b' relative to fl and (2) the presence of peaks f2 and g'.

[0086] Figure 5 Schematic diagram of a plurality of electrochemical cells including a single ion conductive polymer electrolyte of the present technology forming a solid-state battery. DETAILED DESCRIPTION

[0087] definition

[0088] The use of "including," "comprising," or "having," "containing," "involving," and variations thereof herein, is meant to encompass the items listed thereafter as well as optional additional items.

[0089] It must be noted that as used in this specification and the appended claims, unmodified nouns include plural referents unless the context clearly dictates otherwise.

[0090] As used herein, the term "and / or" is considered to specifically disclose each of the two specified features or components with or without the other. For example, "A and / or B" is considered to specifically disclose each of (i) A, (ii) B, and (iii) A and B, just as if each were individually listed herein.

[0091] As used herein, the expression "single ion conducting polymer" is a polymer comprising an immobilized anion as part of its chemical structure. As used herein, the expression "immobilized anion" refers to an anion that does not shift during the charge / discharge cycle of the battery.

[0092] As used herein, the term "substantially" means to a great or significant extent.

[0093] As used herein, the expression "click chemistry" or "click reaction" refers to such a reaction: it is simple; has high efficiency, high yield, and produces stereospecific and easily removable by-products. In addition, such a reaction can be carried out in an easily removable or benign solvent.

[0094] As used herein, the term "about" in the context of a given value or range refers to a value or range that is within 20%, preferably within 10%, and more preferably within 5% of the given value or range.

[0095] The present disclosure is not limited in its application to the details of the arrangement and construction of the components set forth in the following description or illustrated in the accompanying drawings. The present disclosure can have other embodiments and can be practiced or implemented in a variety of ways. In addition, the wording and terminology used herein are for descriptive purposes and should not be considered restrictive.

[0096] Broadly, the present technology relates to methods for producing single ion conducting polymers, the methods comprising grafting a thiol functionalized conductor compound onto a polymer compound to obtain a single ion conducting polymer. Specifically, the thiol functionalized conductor compound is grafted onto the polymer via a thiol-ene "click" reaction. Advantageously, thiol-ene click reactions are simple and efficient. These reactions allow for the creation of a large number of new polymer structures while enabling great spatial and temporal control of the material. Furthermore, in certain embodiments, the thiol functionalized conductor can be grafted onto a polymer having a low Tg, thereby producing a single ion conducting polymer having improved conductivity.

[0097] Thiol-functionalized conductor compounds

[0098] In certain embodiments, the thiol-functionalized conductor compound used in the methods of the present technology comprises: a sulfonimide anion covalently linked at one end, the sulfonimide anion being associated with a monovalent cation; 1 to 3 hydrocarbon chains as linking groups (L); 0 to 2 functional groups (R); and a thiol group at the other end of the compound.

[0099] In some embodiments, the thiol-functionalized conductor compound has Formula I:

[0100]

[0101] In certain embodiments, R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O)m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, where 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2C F 2O) units are randomly copolymerized; or aryl substituted with at least one fluorine and at least one electron withdrawing group. In some embodiments, branched C3-C4 fluoroalkyl includes -CF-(CF3)2, -CF(CF3)-CF2-CF3 and CF2-CF-(CF3)2. In other embodiments, the electron withdrawing group is -CN, -NO2, -CF3 or -SO2CF3. In other embodiments, the aryl compound substituted with at least one fluorine and at least one electron withdrawing group is -C6F4-CF3 or -C6F4-SO2CF3. In yet other embodiments, R f It is CF3.

[0102] In certain embodiments, M in the thiol-functionalized conductor compound + is a monovalent cation. In some embodiments, the monovalent cation is an alkali metal cation. In other embodiments, the alkali metal cation is H + , K + 、Na + , Li + , Rb + or Cs + In yet other embodiments, the alkali metal cation is Li + .

[0103] L1, L2 and L3 in the thiol-functionalized conductor compound are linking groups that at least connect the sulfonyl imide anion at one end of the compound to the thiol group at the other end.

[0104] In certain embodiments, L1 is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide linker, fluorinated ethylene oxide linker, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl. In some embodiments, L1 is n-alkyl, and n is 1, 2, 3, 4, 5 or 6. In other embodiments, L1 is (CH2)3.

[0105] L2 may be absent or present. When present, L2 is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide linking group, fluorinated ethylene oxide linking group, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl. In some embodiments, L2 is n-alkyl, and n is 1, 2, 3, 4, 5 or 6. In other embodiments, L2 is (CH2)2.

[0106] L3 may also be absent or present. When present, L3 is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide linking group, fluorinated ethylene oxide linking group, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl. In some embodiments, L3 is n-alkyl, and n is 2, 3, 4, 5 or 6. In other embodiments, L3 is (CH2)3.

[0107] R1 and R2 in the thiol functionalized conductor compound are functional groups. R2 may be absent or present. R1 and R2 (when present) are each independently an ether, a thioether, an ester, an amide, a carbamate, a urea, a secondary amine, or a tertiary amine. In some embodiments, R1 is an ester. In other embodiments, R2 is a thioether.

[0108] In one embodiment, R f CF3, M + For Li + , L1, L2 and L3 are each n-alkyl, wherein n is 2, 3, 4, 5 or 6, R1 is an ester, and R2 is a thioether. f CF3, M + For Li + , L1 and L3 are (CH2)3, L2 is (CH2)2, R1 is an ester, and R2 is a thioether.

[0109] In certain embodiments, the thiol-functionalized conductor compound has Formula II or Formula III:

[0110]

[0111] In other embodiments, the thiol-functionalized conductor compound has Formula II.

[0112] In other embodiments, the thiol-functionalized conductor compound has Formula III.

[0113] In some embodiments, the thiol-functionalized conductor compound is synthesized by reacting a thiol compound with a lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-monomer having C=C in its backbone. Advantageously, the method comprises a single step, and the direct addition of thiol on the LiTFSI monomer provides a simpler synthetic route than the thiol-functionalized LiTFSI-monomer in which the thiol is directly attached to the LiTFSI via an alkyl chain.

[0114] In certain embodiments, the reaction of a thiol compound with a LiTFSI-monomer having C=C in its backbone is also a thiol-ene "click" reaction.

[0115] In certain embodiments, the C=C in the LiTFSI-monomer is at one end of the LiTFSI-monomer. In some embodiments, the C=C is at one end of the LiTFSI-monomer, and the sulfonimide anion is at the other (opposite) end of the LiTFSI-monomer. In other embodiments, the LiTFSI-monomer has the following formula IV, formula V, formula VI, formula VII, or formula VIII:

[0116]

[0117]

[0118] In certain embodiments, the thiol compound used to synthesize the thiol functionalized conductor compound is n-alkyl dithiol, ethylene glycol-based dithiol, PEO-based dithiol, 2,2'-thiodiethanethiol, 2,3-dimercapto-1-propanol, 1,2-benzene-dithiol, 1,3-benzene-dithiol, 1,4-benzene-dithiol, 1,4, benzenedimethanethiol, toluene-3,4-dithiol, biphenyl-4,4'-dithiol, p-terphenyl-4,4-dithiol, 1,3-propane-dithiol or 2,2'-(ethylenedioxy)diethanethiol. In some embodiments, the n-alkyl dithiol has the formula SH-(CH2) r -SH, wherein r = 2, 3, 4, 5, 6, 8, 9, 11 or 16. In other embodiments, the ethylene glycol-based dithiol has the formula SH-(CH2CH2O) s -CH2CH2-SH, wherein s=2, 3 or 5. In some other embodiments, the PEO-based dithiol has the formula SH-PEO-SH, wherein the number average molecular weight (Mn) of PEO is about 1000, about 1500, about 3400 or about 8000. In other embodiments, the thiol compound is 1,3-propane-dithiol. In some other embodiments, the thiol compound is 2,2'-(ethylenedioxy)diethanethiol. Advantageously, 1,3-propane-dithiol and 2,2'-(ethylenedioxy)diethanethiol are the cheapest dithiols available on the market, which provides an economical way to synthesize SIPE.

[0119] In some embodiments, the thiol-functionalized conductor compound is obtained by reacting an excess of the thiol compound with the LiTFSI-monomer. In other embodiments, the thiol-functionalized conductor compound is obtained by reacting about 1 equivalent to about 4 equivalents of the thiol compound with the LiTFSI-monomer. In still other embodiments, the method comprises reacting about 1 equivalent to about 2 equivalents, about 1 equivalent to about 3 equivalents, about 1.5 equivalents to about 2.5 equivalents, about 1 equivalent to about 1.5 equivalents, about 2 equivalents, or about 1.3 equivalents of the thiol compound with the LiTFSI-monomer.

[0120] In certain embodiments, the thiol-functionalized conductor compound is obtained by reacting the thiol compound and the LiTFSI-monomer in bulk (i.e., in the absence of a solvent). Such an embodiment is reasonable when the reactants are miscible with each other. In other embodiments, the thiol-functionalized conductor compound is obtained by reacting the thiol compound and the LiTFSI-monomer in a solvent. In some embodiments, the solvent is water, methanol, ethanol, isopropanol, anhydrous methyl cyanide (MeCN), tetrahydrofuran (THF), acetone, dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). In some embodiments, the thiol compound and the LiTFSI-monomer are reacted in THF.

[0121] In certain embodiments, reacting the thiol compound and the LiTFSI-monomer comprises dissolving the thiol compound and the LiTFSI-monomer together in a solvent. In other embodiments, reacting the thiol compound and the LiTFSI-monomer comprises dissolving the thiol compound in a first solvent, dissolving the LiTFSI-monomer in a second solvent, and adding the LiTFSI-monomer dissolved in the second solvent to the thiol compound dissolved in the first solvent. In some embodiments, the first solvent and the second solvent are the same solvent. In other embodiments, the first solvent and the second solvent are different solvents. In such embodiments, the two different solvents are miscible with each other. The first solvent and the second solvent can be any solvent disclosed above.

[0122] In certain embodiments, the LiTFSI-monomer dissolved in the second solvent is added slowly and / or dropwise to the thiol compound dissolved in the first solvent. This can prevent temperature jumps and solvent evaporation. However, the addition of reagents is not limited to a specific order. Therefore, it should be understood that in other embodiments, for example, the thiol compound dissolved in the first solvent can be added to the LiTFSI-monomer dissolved in the second solvent. In certain embodiments of the latter embodiment, the thiol compound dissolved in the first solvent can be added slowly and / or dropwise to the LiTFSI-monomer dissolved in the second solvent.

[0123] In certain embodiments, the synthesis of the thiol-functionalized conductor compound does not require a heating step. Specifically, in certain embodiments, the thiol-functionalized conductor compound can be obtained by reacting the thiol compound and the LiTFSI-monomer at a temperature of about 15° C. to about 30° C. In other embodiments, the thiol-functionalized conductor compound is obtained by reacting the thiol compound and the LiTFSI-monomer at a temperature of about 15° C., about 20° C., about 25° C. (room temperature (RT)), or about 30° C. In yet other embodiments, the thiol-functionalized conductor compound is obtained by reacting the thiol compound and the LiTFSI-monomer at a temperature of about 25° C. (RT).

[0124] In other embodiments, the thiol-functionalized conductor compound is obtained by reacting the thiol compound and the LiTFSI-monomer for about 12 hours to about 24 hours. In other embodiments, the thiol-functionalized conductor compound is obtained by reacting the thiol compound and the LiTFSI-monomer for about 14 hours to about 22 hours, about 16 hours to about 20 hours, or about 18 hours. In other embodiments, the thiol-functionalized conductor compound is obtained by reacting the thiol compound and the LiTFSI-monomer for at least about 12 hours.

[0125] In other embodiments, the synthesis of the thiol-functionalized conductor compound includes adding a catalyst to the reaction of the thiol compound and the LiTFSI-monomer. As used herein, the term "catalyst" refers to a substance that can be added to the reaction to increase the reaction rate without being consumed in the process. In certain embodiments, the catalyst is triethylamine (Et3N), diethylamine, di-n-propylamine, C2-C6 primary amine, N, NO, NO-tetramethyl 1,8-naphthalenediamine (proton sponge, (proton sponge, PS)), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), tripropyl phosphine, dimethylphenylphosphine, diphenylmethylphosphine or triphenylphosphine. In some embodiments, the catalyst is Et3N. In other embodiments, the catalyst is added in an amount of about 0.05 mol% to about 30 mol%.

[0126] In other embodiments, the synthesis of the thiol-functionalized conductor compound includes adding a free radical initiator to the reaction of the thiol compound with the LiTFSI-monomer. As used herein, the expression "free radical initiator" refers to a substance that can generate free radical species and promote free radical reactions under mild conditions. As used herein, the expression "free radical species" refers to uncharged molecules with unpaired valence electrons, which are generally highly reactive and short-lived. In the synthesis of the thiol-functionalized conductor compound, the free radical initiator can be used to generate thiol radicals from the thiol compound and / or complete the reaction between the thiol compound and the LiTFSI-monomer. In some embodiments, the free radical initiator used is a thermally activated free radical initiator. In other embodiments, the free radical initiator is a photochemically activated free radical initiator. In other embodiments, the free radical initiator is azobisisobutyronitrile (AIBN), benzyl peroxide, 4,4′-azobis(4-cyanovaleric acid) (ACVA), 2,2-dimethoxy-2-phenylacetophenone (DMPA, Irgacure 651), 2-hydroxy-2-methylpropiophenone (Irgacure 1173), or 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959).

[0127] In other embodiments, the free radical initiator is added in an amount of about 0.05 mol% to about 5 mol%, about 0.1 mol% to about 2 mol%, or about 0.5 mol% to about 1 mol%.

[0128] In other embodiments, the free radical initiator is photochemically activated by UV light. In some embodiments, the wavelength of UV light is about 250nm to about 450nm, about 300nm to about 400nm or about 365nm. In other embodiments, the free radical initiator is photochemically activated for about 1 minute to about 2 hours, about 5 minutes to about 1 hour, about 10 minutes to about 40 minutes, about 10 minutes to about 50 minutes, about 15 minutes to about 45 minutes, or about 30 minutes. In some other embodiments, the free radical initiator is DMPA, which is added in an amount of about 0.5mol% to about 1mol%, and is irradiated with UV light for a duration of about 10 minutes to about 40 minutes. In other embodiments, the free radical initiator is DMPA, which is added in an amount of about 0.5mol% to about 1mol%, and is irradiated with UV light for a duration of about 30 minutes with a wavelength of about 365nm.

[0129] In certain embodiments, in the step of dissolving the thiol compound in the first solvent, in the step of dissolving the LiTFSI-monomer in the second solvent, in both the step of dissolving the thiol compound in the first solvent and dissolving the LiTFSI-monomer in the second solvent, or in the step of dissolving the thiol compound and the LiTFSI-monomer in the solvent together, any one or more of a catalyst or a free radical initiator or a combination thereof may be added to the reaction of the thiol compound and the LiTFSI-monomer. In some embodiments, a catalyst is added in the step of dissolving the thiol compound in the first solvent. In other embodiments, a free radical initiator is added in the step of dissolving the thiol compound and the LiTFSI-monomer in the solvent together.

[0130] Advantageously, as through 1 H-NMR spectra (Fig. Figure 3 ), the above disclosed method for synthesizing thiol-functionalized conductor compounds produces a monosubstituted thiol-functionalized conductor compound as its major product. This product can be easily purified to isolate it. Therefore, in certain embodiments, the method for synthesizing thiol-functionalized conductor compounds disclosed herein further comprises precipitating the thiol-functionalized conductor compound. In certain embodiments, the precipitation of the thiol-functionalized conductor compound is carried out in hexane, pentane, cyclohexane, octane, or diethyl ether. Advantageously, the thiol compound used in the synthesis of the thiol-functionalized conductor compound is soluble in such a solvent, thereby allowing the excess thiol compound to be substantially removed in the precipitation step.

[0131] polymer

[0132] In certain embodiments, the polymer compound used in the methods of the present technology is an unmodified commercial polymer. In some embodiments, the unmodified commercial polymer is a polymer based on poly(ethylene oxide) (PEO). Advantageously, the PEO-based single-ion polymer obtained by the methods of the present technology is comparable to the classic PEO / LiTFSI salt in the polymer electrolyte, but has a much higher lithium migration number. In some cases, the PEO-based polymer is PEO methyl ether acrylate, PEO diacrylate, or poly(allyl glycidyl ether) (PAGE). In some embodiments, depending on the position of the C=C double bond on the polymer, the thiol-functionalized single-ion conductor compound can be grafted on one end, both ends, or on the side chain of the PEO-based polymer. Therefore, in some embodiments, the thiol-functionalized single-ion conductor compound is grafted on one end of the PEO methyl ether acrylate. In other embodiments, the thiol-functionalized single-ion conductor compound is grafted on both ends of the PEO diacrylate. In yet other embodiments, the thiol-functionalized single ion conductor compound is grafted onto the side chains of the PAGE homopolymer. In some embodiments, PAGE can be synthesized via anionic ring-opening polymerization, and the C=C double bond on the side chain can be used for the thiol-ene connection of the thiol-functionalized single ion conductor compound. Therefore, in certain embodiments, the PAGE polymer can include a thiol-functionalized single ion conductor compound grafted onto each of its side chains (see, e.g., Formula C below). In other embodiments, the PAGE monomer can also be partially grafted, for example to include a first side chain containing an allyl ether group and a second side chain onto which a thiol-functionalized single ion conductor compound is grafted (see, e.g., Formula D below).

[0133] In other embodiments, the unmodified commercial polymer used in the method of the present technology can be a butadiene-derived polymer. Butadiene-derived polymers are one of the most common commercial polymers, which are used in the automotive, aviation and personal protection industries. The butadiene block has a C=C double bond that can be used for thiol-ene reactions. In certain embodiments, the butadiene-derived polymer is poly(acrylonitrile-co-butadiene) (PAN-co-PB), poly(1,4-butadiene) or poly(1,2-butadiene). In other embodiments, the butadiene-derived polymer is polyPAN-co-PB. Advantageously, the polar acrylonitrile unit of PAN-co-PB has a strong dipole interaction that is conducive to salt dissociation and is suitable for high-voltage cathode materials. In yet other embodiments, the butadiene-derived polymer is poly(1,2-butadiene).

[0134] In certain embodiments, the thiol-functionalized single ion conductor compound can be grafted at any position on the butadiene-derived monomers listed above, depending on the position of the C=C double bond on the molecule. Thus, the thiol-functionalized single ion conductor can be grafted on the main chain, on the side chain, or on both the main chain and the side chain of the butadiene-derived monomer. In some embodiments, the thiol-functionalized single ion conductor compound is grafted on the side chain of a PAN-co-PB monomer. In some cases, one thiol-functionalized single ion conductor compound is grafted on the main chain of a PAN-co-PB monomer, and at least one additional thiol-functionalized single ion conductor compound is grafted on the side chain of a PAN-co-PB monomer.

[0135] In certain embodiments, the commercial polymer is a polymer derived from polyvinyl alcohol (PVA). The starting polymer is fully or partially hydrolyzed PVA, and the side OH groups can be modified to become side acrylate groups or side methacrylate groups. The acrylation reaction can be carried out by reacting the OH with acryloyl chloride or methacryloyl chloride. The thiol-functionalized single ion conductor can then be grafted onto the C=C double bond on the side chain of the PVA-derived polymer. The following formula H represents an implementation of such an embodiment.

[0136] In other embodiments, the commercial polymer is a polymer based on polyvinylidene difluoride (PVDF). PVDF is one of the most important polymers for battery applications due to its strong binding ability and its good electrochemical stability. In some embodiments, the PVDF-based polymer is a modified PVDF-based polymer. In certain embodiments of these embodiments, the modified PVDF-based polymer is a modified PVDF, a modified polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-CTFE), or a modified polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) monomer. In some embodiments, the PVDF-based polymer is modified by dehydrochlorination or dehydrofluorination of a C=C double bond on the polymer backbone with a base. After this modification, the thiol-functionalized single ion conductor compound can then be reacted with the C=C double bond on the modified PVDF backbone to complete the grafting of the single ion conductor to the polymer. Bases suitable for modifying PVDF include, but are not limited to, inorganic bases such as KOH, NaOH, LiOH, and CsOH, and organic amine basic compounds such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetrabutylammonium hydroxide (TBAOH), potassium tert-butoxide (TBuOK), and Et3N.

[0137] In other embodiments, the polymer compound used in the method of the present technology is cellulose. Cellulose is particularly suitable as a polymer compound due to its wide availability and low price. In some embodiments, the cellulose is a modified cellulose. Specifically, allyl bromide can be used to modify the hydroxyl groups on the cellulose to produce C=C double bonds along the cellulose backbone and allow the thiol-functionalized single ion conductor to be grafted.

[0138] In yet other embodiments, the polymer compound is an unsaturated polyester resin (UPR). In certain of these embodiments, the UPR can be made from maleic anhydride and butanediol.

[0139] Grafting reaction conditions

[0140] In certain embodiments, grafting of the thiol-functionalized conductor compound onto the polymer compound comprises mixing about 1 to about 4 equivalents of the thiol-functionalized conductor compound relative to the molar amount of C=C on the polymer compound. In some embodiments, grafting comprises mixing about 1 to about 3 equivalents, about 1.5 to about 2.5 equivalents, or about 2 equivalents of the thiol-functionalized conductor compound with the polymer compound.

[0141] In certain embodiments, the methods of the present technology include mixing the thiol-functionalized conductor compound and the polymer compound in bulk (i.e., in the absence of a solvent). Such embodiments are reasonable when the reactants are miscible with each other. In other embodiments, the methods of the present technology include mixing the thiol-functionalized conductor compound and the polymer compound together in a solvent. In still other embodiments, the thiol-functionalized conductor compound and the polymer compound can be mixed together in bulk before being added to the solvent.

[0142] In some embodiments, the solvent is an anhydrous solvent. In other embodiments, the solvent is an aqueous solvent. In yet other embodiments, the solvent can be a mixture of an aqueous solvent and an anhydrous solvent, wherein the aqueous solvent and the anhydrous solvent are miscible with each other. In other embodiments, the solvent is water, methanol, ethanol, isopropanol, butanol, N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), acetonitrile (MeCN), tetrahydrofuran (THF), acetone, dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) or a combination thereof. In yet other embodiments, the solvent is THF or DMF.

[0143] In other embodiments, the methods of the present technology include mixing a thiol-functionalized conductor compound and a PEO-based polymer matrix and adding to THF or DMF. In yet other embodiments, the methods include mixing a thiol-functionalized conductor compound and a butadiene-derived monomer in THF or DMF. In yet other embodiments, the methods include mixing a thiol-functionalized conductor compound and a modified PVDF-based polymer in NMP or DMF. In yet other embodiments, the methods include mixing a thiol-functionalized conductor compound and a modified cellulose in DMAc. In yet other embodiments, the methods include mixing a thiol-functionalized conductor compound and a modified cellulose in DMAc and LiCl.

[0144] In certain embodiments, the methods of the present technology do not require a heating step. In certain implementations of these embodiments, the grafting of the thiol-functionalized conductor compound onto the polymer compound is therefore performed at a temperature of about 15°C to about 30°C. In other embodiments, the method includes grafting the thiol-functionalized conductor compound onto the polymer compound at a temperature of about 18°C ​​to about 28°C, about 22°C to about 27°C, or about 25°C (i.e., room temperature (RT)). In some embodiments, the method includes grafting the thiol-functionalized conductor compound onto the polymer compound at a temperature of about 25°C (RT).

[0145] In other embodiments, the method of the present technology includes grafting a thiol-functionalized conductor compound onto a polymer compound in the presence of a catalyst. As used herein, the term "catalyst" refers to a substance that can be added to a reaction to increase the reaction rate without being consumed in the process. In certain embodiments, the catalyst is selected from triethylamine (Et3N), diethylamine, di-n-propylamine, C2 to C6 primary amines, N,N,N',N'-tetramethyl-1,8-naphthalenediamine (proton sponge, (proton sponge, PS)), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), tripropyl phosphine, dimethylphenyl phosphine, diphenylmethyl phosphine, or triphenyl phosphine. In other embodiments, the catalyst is added in an amount of about 0.05 mol% to about 30 mol%.

[0146] In other embodiments, the method includes grafting a thiol-functionalized conductor compound onto a polymer compound in the presence of a free radical initiator. As used herein, the expression "free radical initiator" refers to a substance that can generate free radical species and promote free radical reactions. As used herein, the expression "free radical species" refers to an uncharged molecule with unpaired valence electrons, which is generally highly reactive and short-lived. Without being bound by theory, the free radical initiator used in the method of the present technology generates free radicals after being activated, and the free radicals deprotonate the thiol in the thiol-functionalized conductor compound to produce thiol radicals. The thiol radicals are added to the C=C double bond in the polymer compound and form a carbon-centered free radical. Then, the free radical chain is transferred to a new thiol and a new thiol radical is generated. The cycle continues until all thiols react with olefins and the reaction is completed.

[0147] In some embodiments, the free radical initiator is a thermally activated free radical initiator. In such embodiments, the method includes a heating step. Therefore, in certain embodiments of these embodiments, the method includes grafting the thiol-functionalized conductor compound to the polymer compound at a temperature of about 40°C to about 80°C, about 50°C to about 70°C, about 60°C to about 70°C, about 60°C to about 65°C, about 65°C, or about 60°C. Examples of thermally activated free radical initiators suitable for the methods of the present technology include, but are not limited to, 2,2′-azobis(2-methylpropionitrile) (AIBN), benzyl peroxide, and 4,4′-azobis(4-cyanovaleric acid) (ACVA). In some embodiments, the thermally activated free radical initiator is AIBN.

[0148] In certain embodiments, the free radical initiator is a photochemically activated free radical initiator. Examples of photochemically activated free radical initiators suitable for use in the methods of the present technology include, but are not limited to, 2,2-dimethoxy-2-phenylacetophenone (DMPA, Irgacure 651), 2-hydroxy-2-methylpropiophenone (Irgacure 1173), or 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959). In some embodiments, the photochemically activated free radical initiator is DMPA.

[0149] In certain embodiments, the free radical initiator is activated by high energy light. In other embodiments, the high energy light can be UV light. In some embodiments, the wavelength of the UV light is about 250nm to about 450nm, about 300nm to about 400nm, or about 365nm.

[0150] In other embodiments, the free radical initiator is photochemically activated for a period of about 1 minute to about 2 hours, about 5 minutes to about 1 hour, about 10 minutes to about 40 minutes, about 15 minutes to about 35 minutes, about 20 minutes, or about 30 minutes.

[0151] In yet other embodiments, the free radical initiator is added in an amount of about 0.05 mol% to about 5 mol%, about 0.1 mol% to about 2 mol%, or about 0.5 mol% to about 1 mol%.

[0152] In certain embodiments, in the step of mixing the thiol-functionalized conductor compound and the polymer compound in bulk, or mixing the thiol-functionalized conductor compound and the polymer compound together in a solvent, any one or more of a catalyst or a free radical initiator or a combination thereof may be added to the reaction of the thiol-functionalized single ion conductor compound and the polymer compound.

[0153] In certain embodiments, after the C=C bonds are completely consumed, the grafting reaction mixture may contain excess unreacted thiol-functionalized single ion conductor compounds and must be removed because the free thiol groups will react with lithium metal. Therefore, in some embodiments, the method of the present technology also includes a purification step. In some embodiments, the purification step can be completed using dialysis. The solution can be dialyzed against a polar solvent to remove excess thiol-functionalized single ion conductor compounds. In such embodiments, the dialysis solvent can be DI water, MeOH, EtOH, IPA, acetone, acetonitrile, THF, or any combination thereof. In some embodiments, the dialysis bag can be a regenerated cellulose bag. The molecular weight cutoff of the dialysis bag can be about 1 kDa, about 2 kDa, about 3.5 kDa, about 8 kDa, about 10 kDa, about 15 kDa, about 25 kDa, or about 50 kDa. In one embodiment, the molecular weight cutoff of the dialysis bag is about 3.5 kDa. Alternatively, the excess thiol-functionalized single ion conductor compound can be removed by precipitation into DI water, MeOH, EtOH, IPA, acetone, acetonitrile, THF, or any combination thereof. Alternatively, the excess thiol-functionalized single ion conductor compound can be removed by purification via silica gel column chromatography.

[0154] The obtained single ion conductive polymer

[0155] In certain embodiments, the single ion conducting polymer obtained by the methods of the present technology has Formula A:

[0156]

[0157] Where R f F; CF3; CF2CF3; (CF2)n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; and

[0158] M + It is a monovalent cation.

[0159] In other embodiments, the single ion conducting polymer has Formula B:

[0160]

[0161] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0162] M + is a monovalent cation; and

[0163] Where 3≤n≤50.

[0164] In yet other embodiments, the single ion conducting polymer has Formula C:

[0165]

[0166] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q-CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0167] M + is a monovalent cation; and

[0168] Where 5≤n≤500.

[0169] In other embodiments, the single ion conducting polymer has the formula D:

[0170]

[0171] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0172] M + It is a monovalent cation;

[0173] 1≤m≤500;

[0174] 1≤n≤500; and

[0175] 2≤m+n≤1000.

[0176] In yet other embodiments, the single ion conducting polymer has Formula E:

[0177]

[0178] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q-CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0179] M + It is a monovalent cation;

[0180] 1≤m≤500;

[0181] 1≤n≤500;

[0182] 1≤l≤500; and

[0183] 3≤m+n+l≤1500.

[0184] In other embodiments, the single ion conducting polymer has Formula F:

[0185]

[0186] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0187] M + is a monovalent cation; and

[0188] 5≤n≤500.

[0189] In yet other embodiments, the single ion conducting polymer has the formula G:

[0190]

[0191] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q-CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0192] M + is a monovalent cation; and

[0193] 5≤n≤500.

[0194] In other embodiments, the single ion conducting polymer has the formula H:

[0195]

[0196] Wherein R is H or CH3;

[0197] 1≤m≤6000;

[0198] 0≤n≤1500;

[0199] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0200] M + It is a monovalent cation.

[0201] In yet other embodiments, the single ion conducting polymer has Formula I:

[0202]

[0203] Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q-CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0204] M + It is a monovalent cation;

[0205] 10≤m≤3000; and

[0206] 50≤n≤6000.

[0207] In some embodiments, the single ion conducting polymer has Formula J:

[0208]

[0209] Where R is H + , allyl, or a combination thereof, and

[0210] At least one R is

[0211] Where R f F; CF3; CF2CF3; (CF2) n CF3 wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether group, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0212] M + is a monovalent cation; and

[0213] wherein 100≤n≤6000. In certain embodiments of this embodiment, allyl is (—CH 2 —CH═CH 2 ).

[0214] In other embodiments, the single ion conducting polymer has the formula K:

[0215]

[0216] wherein R is a linear C2 to C6 alkyl group or a branched C3 to C6 alkyl group;

[0217] R f F; CF3; CF2CF3; (CF2) nCF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and (CF2O) units and (CF2CF2O) units are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group;

[0218] M + is a monovalent cation; and

[0219] 5≤n≤100.

[0220] In certain embodiments of the single ion conducting polymer disclosed above, the branched C3-C4 fluoroalkyl group includes -CF-(CF3)2, -CF(CF3)-CF2-CF3 and CF2-CF-(CF3)2. In other embodiments, the electron withdrawing group is selected from -CN, -NO2, -CF3 and -SO2CF3. In other embodiments, the aromatic compound substituted with at least one fluorine and at least one electron withdrawing group is -C6F4-CF3 or -C6F4-SO2CF3. In still other embodiments, R f It is CF3.

[0221] In certain embodiments, the monovalent cation is an alkali metal cation. In other embodiments, the alkali metal cation is H+, K+, Na+, Li+, Rb+, or Cs+. In yet other embodiments, the alkali metal cation is Li+.

[0222] In other embodiments, the single ion conducting polymer is:

[0223]

[0224] Where 3≤n≤50; Where 5≤n≤500;

[0225] Where 1≤m≤500, 1≤n≤500, and 2≤m+n≤1000;

[0226] Where 1≤m≤500, 1≤n≤500, 1≤l≤500, and 3≤m+n+l≤1500;

[0227] Where 5≤n≤500; Where 5≤n≤500;

[0228] Where R is CH3, 1≤m≤6000, and 0≤n≤1500; Where 10≤m≤3000; and 50≤n≤6000; Where R is: H + , allyl or a combination thereof,

[0229] At least one R is as well as

[0230] 100 ≤ n ≤ 6000; or

[0231] Where 5≤n≤100.

[0232] In other embodiments, the method of the present technology further comprises adding a lithium-containing alkaline compound after the reaction is complete to remove any residual triethylamine in the thiol-functionalized single ion conductor compound used. In some embodiments, the addition of the lithium-containing alkaline compound precedes the above-mentioned precipitation step. In other embodiments, the lithium-containing alkaline compound can be selected from Li2CO3, LiOH, LiH, Li2SO3, Li3PO4, lithium acetate and lithium formate, and combinations thereof. In yet other embodiments, the lithium-containing alkaline compound is LiH.

[0233] In certain embodiments, the mass yield of single-ion conducting polymers obtained by the methods of the present technology is at least about 40%, about 40% to about 90%, about 45% to about 70%, about 55% to about 70%, about 55% to about 65%, about 46%, about 58%, about 62%, or about 85%.

[0234] Solid-state batteries

[0235] From another aspect, the present technology is directed to a solid-state battery having a plurality of electrochemical cells, each electrochemical cell including a positive electrode, a negative electrode, and an electrolyte layer disposed therebetween. Figure 4A solid-state battery 10 having a plurality of electrochemical cells 12 is schematically shown, each of which includes an anode or negative electrode film 14, a solid electrolyte 16, and a cathode or positive electrode film 18 stacked on a current collector 20. The solid electrolyte 16 typically contains a lithium salt to provide ion conduction between the anode 14 and the cathode 18. In some embodiments, the anode film 14 is made of a metallic lithium sheet having a thickness ranging from about 20 microns to about 100 microns. In other embodiments, the thickness of the solid electrolyte 16 ranges from about 5 microns to about 50 microns. In other embodiments, the thickness of the positive electrode film 18 ranges from about 20 microns to about 100 microns. The single-ion conductive polymer of the present technology can be integrated in the anode film 14, the solid electrolyte 16, or the cathode film 18.

[0236] In certain embodiments, the lithium salt contained in the solid electrolyte 16 may be LiCF3SO3, LiB(C2O4)2, LiN(CF3SO2)2, LiN(FSO2)2, LiC(CF3SO2)3, LiC(CH3)(CF3SO2)2, LiCH(CF3SO2)2, LiCH2(CF3SO2), LiC2F5SO3, LiN(C2F5SO2)2, LiN(CF3SO2), LiB(CF3SO2)2, LiPF6, LiSbF6, LiClO4, LiSCN, LiAsF6, or LiBF4.

[0237] The internal operating temperature in the electrochemical cell 12 of the battery 10 is typically about 40° C. to about 100° C. The lithium polymer battery preferably includes an internal heating system to allow the electrochemical cell 12 to reach its optimal operating temperature. The battery 10 can be used indoors or outdoors in a wide temperature range (about -40° C. to about +70° C.).

[0238] In certain embodiments, the lithium migration number of the single ion polymer electrolyte of the present technology is greater than about 0.8, greater than about 0.85, greater than about 0.9, greater than about 0.95, greater than about 0.99, or about 1.0. In such embodiments, only lithium cations contribute to the charge / discharge current. This allows uniform lithium deposition and minimizes dendrite growth, which increases the life cycle of the Li battery. Such a single ion conducting polymer electrolyte can serve as both a lithium ion source and a matrix for the polymer electrolyte, which eliminates the blending process in the prior art where the polymer electrolyte is a mixture of PVDF, PEO, and a lithium salt.

[0239] Example

[0240] The following examples are given to illustrate the practice of various embodiments of the present disclosure. They are not intended to limit or define the entire scope of the present disclosure.

[0241] Example 1: Synthesis of a thiol-functionalized single ion conductor compound according to one embodiment of the present technology

[0242] In brief, in a dried round-bottom flask, 1,3, propanedithiol (2.12 g, 19.6 mmol, Sigma-Aldrich, >99%) was dissolved in 20 mL of anhydrous THF (Sigma-Aldrich). The solution was purged with argon for about 40 minutes (min) and then cooled to 0 ° C. Triethylamine (0.45 g, 4.53 mmol, Sigma-Aldrich, >99%) was dissolved in 2 mL of anhydrous THF and added to a flask. Then 1-[3-(acryloyloxy)-propylsulfonyl]-1-(trifluoromethylsulfonyl) lithium imide (J503, 5.0 g, 15.1 mmol) was dissolved in 15 mL of anhydrous THF and added dropwise to a flask. The reaction was stirred and warmed to room temperature overnight (about 18 hours (h)). After the reaction, THF was evaporated and the crude product was precipitated into 200 mL of hexane four times to remove excess dithiol. The viscous liquid product was collected and dried on a rotary evaporator. About 3.7 g of transparent light yellow viscous J517 was obtained (85% yield).

[0243] The synthetic route for preparing thiol-functionalized single ion conductors according to this embodiment is as follows:

[0244]

[0245] Example 2: Synthesis of a thiol-functionalized single ion conductor compound according to another embodiment of the present technology

[0246] 1,3-Propanedithiol (0.52 g, 4.8 mmol), 1-[3-(acryloyloxy)-propylsulfonyl]-1-(trifluoromethylsulfonyl)imide lithium (J503, 0.79 g, 2.4 mmol), photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA, 8 mg, 0.03 mmol, Sigma-Aldrich, 99%) were dissolved in 5 mL of anhydrous THF. The solution was purged with argon for 20 minutes and irradiated with a 365 nm UV lamp (VWR) for 30 minutes at room temperature with stirring. After the reaction, THF was evaporated and the crude product was washed four times with hexane and then dried in vacuo at 100 ° C for about 2 hours. Finally, 0.85 g of a transparent light yellow liquid (80% yield) was obtained.

[0247] The synthetic route for preparing thiol-functionalized single ion conductors according to this embodiment is as follows:

[0248]

[0249] Example 3: Grafting of Thiol-Functionalized Single Ion Conductor Compounds onto PEO-Based Polymers

[0250] A thiol-functionalized single ion conductor (J517) according to one embodiment was grafted onto PEO methyl ether acrylate, PEO diacrylate, and poly(allyl glycidyl ether) (PAGE) homopolymers.

[0251] Briefly, thiol functionalized single ion conductor J517 (1.84 g, 4.2 mmol), poly (ethylene glycol) methyl ether acrylate (480 g / mol, Sigma-Aldrich, 1.34 g, 2.8 mmol) and DMPA (7 mg, 0.028 mmol) were mixed and degassed with Ar. Then, 5 mL of anhydrous THF was added to dissolve the mixture. The solution was irradiated with 365 nm UV (VWR UV hand lamp) at room temperature for 20 minutes under stirring. After the reaction, LiH was added to remove the residual triethylamine in J517. The mixture was filtered and precipitated into hexane three times to wash away Et3N. The sticky solid was vacuum dried at 50°C for 24 hours, and 2.71 g of product (85% yield) was obtained. 1H-NMR did not show vinyl protons from PEG-methyl ether acrylate, and the final product was a mixture of P230 and J517 in a 2: 1 molar ratio.

[0252] The synthetic route for grafting thiol-functionalized single ion conductors onto PEO methyl ether acrylate is shown below:

[0253]

[0254] A similar synthesis was performed with PEO diacrylate. Briefly, J517 (5.2 g, 11.8 mmol), poly(ethylene glycol) diacrylate (700 g / mol, Sigma-Aldrich, 4.1 g, 5.9 mmol) and DMPA photoinitiator (15 mg, 0.06 mmol) were dissolved in 12 mL of anhydrous THF. The solution was purged with Ar for 30 min and irradiated with 365 nm UV light (VWR UV hand lamp) for 30 min at room temperature. After the reaction, 1 H-NMR showed no vinyl protons. The product was further purified by silica gel flash chromatography (eluent distribution: DCM to DCM: methanol about 9:1 volume ratio) to remove impurities. The product P231 was collected and dried under vacuum at 60°C for 18 hours to give 5.4 g of a clear light yellow viscous liquid (58% yield).

[0255] The synthetic route for grafting thiol-functionalized single ion conductors onto PEO diacrylate is shown below:

[0256]

[0257] A similar synthesis was performed using PAGE. The synthetic route for grafting thiol-functionalized single ion conductors onto PAGE is shown below:

[0258]

[0259] Example 4: Grafting of a thiol-functionalized single ion conductor compound onto poly(acrylonitrile-co-butadiene)

[0260] (PAN-co-PB) and poly(1,2-butadiene).

[0261] A thiol-functionalized single ion conductor (J517) according to one embodiment was grafted onto PAN-co-PB. Briefly, PAN-co-PB (Sigma-Aldrich, 37 wt% to 39 wt% acrylonitrile content, 0.17 g, 1.92 mmol C=C bonds), J517 (1.68 g, 3.8 mmol) and DMPA (2 mg, 0.008 mmol) were completely dissolved in 8 mL of anhydrous DMF. The solution was purged with Ar for 25 minutes and irradiated with 365 nm UV (VWR UV hand lamp) for 30 minutes. The solution was then precipitated into ether, and the bottom oily liquid was collected and further precipitated into deionized water. The white solid polymer was filtered, washed twice with water, and dried in vacuo at room temperature for 5 hours. 1H NMR showed that 4 mol% of the C=C double bonds reacted with J517, and most of the reacted butadiene units were 1,2-butadiene units.

[0262] The synthetic route for grafting thiol-functionalized single ion conductors onto PAN-co-PB is shown below:

[0263]

[0264] A thiol-functionalized single ion conductor (J517) according to one embodiment was grafted onto poly(1,2-butadiene) to prepare P243. Briefly, two poly(1,2-butadiene)s with different molecular weights were used for synthesis. In the first example, poly(1,2-butadiene) (Mn=1200 g / mol, Nisso America, 0.12 g, 2.24 mmol vinyl), J517 (1.19 g, 2.71 mmol) and DMPA photoinitiator (6 mg, 0.023 mmol) were completely dissolved in 3 mL of anhydrous THF. The solution was purged with Ar for 20 minutes and irradiated with 365 nm UV for 30 minutes. After the reaction, THF was evaporated and the crude product was completely soluble in methanol, indicating that the grafting was successful because poly(1,2-butadiene) was insoluble in methanol. The crude product was dialyzed for 2 days against pure methanol to remove excess J517. Fresh solvent was replaced twice during a 2-day period. The dialysis bag was made of regenerated cellulose and the molecular weight cutoff was 3.5 kDa (Spectra / Por 3RC dialysis membrane). After dialysis, the polymer solution was concentrated and vacuum dried at 80°C for 2.5 hours to obtain 0.45 g of a transparent, colorless, viscous solid (41% yield). In a second example, a higher molecular weight poly(1,2-butadiene) (Mn=2100 g / mol, Nisso America, 0.12 g, 2.24 mmol vinyl), J517 (1.22 g, 2.79 mmol) and DMPA photoinitiator (6 mg, 0.023 mmol) were completely dissolved in 3 mL of anhydrous THF. The solution was purged with Ar for 20 minutes, irradiated with 365 nm UV light for 30 minutes, and purified by dialysis using the same procedure described above. After vacuum drying at 80°C for 2.5 hours, 0.69 g of a transparent, colorless, very viscous solid (62% yield) was obtained.

[0265] The synthetic route for grafting thiol-functionalized single ion conductors onto poly(1,2-butadiene) is shown below:

[0266]

[0267] Example 5: Grafting of thiol-functionalized single ion conductor compounds onto modified PVDF

[0268] A thiol-functionalized single ion conductor (J517) according to one embodiment was grafted onto PVDF modified via dehydrochlorination.

[0269] In brief, modified PVDF is prepared by treating PVDF-CTFE (polyvinylidene fluoride-co-chlorotrifluoroethylene 80 / 20 weight ratio, PolyK) with Et3N. PVDF-CTFE (0.28g, 0.49mmol Cl) is completely dissolved in 5mL NMP, and Et3N (0.25g, 2.44mmol) is added. The solution is stirred at 50°C for 24 hours and precipitated into a mixture of 3mL 1M HCl+75mL deionized water. The light brown solid is redissolved in acetone overnight and precipitated into water again. The solid is collected and vacuum dried at 50°C for 24 hours. FTIR shows a characteristic C=C peak at about 1722cm-1, and 1H NMR shows vinyl protons (about 6.4ppm). NMR integration shows that about 61% of Cl is eliminated to produce C=C bonds.

[0270] The synthesis step of LiTFSI-grafted PVDF (P242) was started by dissolving P241 (1.14 g, about 1.9 mmol C=C bonds) in 10 mL NMP and stirring overnight. The light brown polymer solution was degassed with Ar. J517 (1.0 g, 2.3 mmol) and DMPA photoinitiator (4 mg, 0.016 mmol) were dissolved in 2.5 mL NMP and added to the P241 solution. The reaction mixture was further degassed with Ar and irradiated with 365 nm UV light for 30 minutes. After the reaction, the solution was precipitated into 200 mL deionized water, and the water was decanted. The solid was further washed three times with deionized water. The solid was dried under vacuum at 60 ° C for 18 hours to obtain 0.92 g of polymer product (46% yield).

[0271] The synthetic route for modifying PVDF and grafting thiol-functionalized single ion conductors onto the modified PVDF is shown below.

[0272]

[0273] Example 6: Grafting of thiol-functionalized single ion conductor compounds onto cellulose

[0274] A thiol-functionalized single ion conductor (J517) according to one embodiment was grafted onto cellulose modified with allyl bromide to generate C=C bonds along the cellulose backbone.

[0275] The synthetic route for modifying cellulose and grafting thiol-functionalized single ion conductors onto the modified cellulose is as follows:

[0276]

[0277] Those skilled in the art will think of variations and modifications after reading this disclosure. The disclosed features can be implemented in any combination and sub-combination (including multiple subordinate combinations and sub-combinations) with one or more other features described herein. The multiple features described or illustrated above (including any components thereof) can be combined or integrated in other systems. In addition, certain features can be omitted or not implemented. Those skilled in the art can determine examples of variations, substitutions, and changes, and can do so without departing from the scope of the information disclosed herein.

[0278] It should be understood that the present technology is not limited to the particular embodiments described and illustrated herein, but encompasses all modifications and variations coming within the scope of the present technology as defined in the appended claims.

[0279] All references cited in this specification and their references are incorporated herein by reference in their entirety, to the extent applicable to teach additional or alternative details, features and / or technical background.

Claims

1. A method for producing a single ion conducting polymer, the method comprising grafting a thiol functionalized conductor compound onto a polymer compound to obtain a single ion conducting polymer.

2. The method of claim 1, wherein the thiol-functionalized conductor compound has Formula I: in: R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + It is a monovalent cation; L1 is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide linking group, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl; L2 is absent or present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, oxyethylene linking group, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl; L3 is absent or present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide linking group, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl; R1 is ether, thioether, ester, amide, carbamate, urea, secondary amine or tertiary amine; and R2 is absent or present, and when present is an ether, thioether, ester, amide, carbamate, urea, secondary amine or tertiary amine.

3. The method according to claim 2, wherein R f It is CF3.

4. The method according to claim 2, wherein the electron withdrawing group is -CN, -NO2, -CF3 or -SO2CF3. The method according to claim 2 , wherein the monovalent cation is an alkali metal cation.

6. The method according to claim 5, wherein the alkali metal cation is H + , K + 、Na + , Li + , Rb + or Cs + .

7. The method according to claim 5 or claim 6, wherein the alkali metal cation is Li + .

8. The method according to any one of claims 2 to 7, wherein L1 is n-alkyl, and n is 1, 2, 3, 4, 5 or 6.

9. The method according to claim 8, wherein L1 is (CH2)3.

10. The method according to any one of claims 2 to 9, wherein L2 is n-alkyl, and n is 1, 2, 3, 4, 5 or 6.

11. The method of claim 10, wherein L2 is (CH2)2.

12. The method according to any one of claims 2 to 11, wherein L3 is n-alkyl, and n is 2, 3, 4, 5 or 6.

13. The method of claim 12, wherein L3 is (CH2)3.

14. The process according to any one of claims 2 to 13, wherein R1 is an ester.

15. The process according to any one of claims 2 to 14, wherein R2 is a thioether.

16. The method according to any one of claims 2 to 15, having formula II or formula III:

17. The method of claim 1, wherein the polymer compound is a poly(ethylene oxide) (PEO)-based polymer.

18. The method of claim 17, wherein the PEO-based polymer is PEO methyl ether acrylate, PEO diacrylate, or poly(allyl glycidyl ether) (PAGE) homopolymer.

19. The method according to claim 18, wherein the thiol-functionalized single ion conductor compound is grafted onto one end of the PEO methyl ether acrylate or onto both ends of the PEO diacrylate.

20. The method of claim 18, wherein the thiol-functionalized single ion conductor compound is grafted onto the side chain of the PAGE homopolymer.

21. The method of claim 1, wherein the polymer compound is a butadiene-derived polymer.

22. The method of claim 21, wherein the butadiene-derived polymer is poly(acrylonitrile-co-butadiene) (PAN-co-PB), poly(1,4-butadiene), or poly(1,2-butadiene).

23. The method of claim 22, wherein the thiol-functionalized single ion conductor compound is grafted on the side chain of the PAN-co-PB.

24. The method of claim 22, wherein the butadiene-derived polymer is poly(1,2-butadiene).

25. The method of claim 1, wherein the polymer compound is a polyvinylidene fluoride (PVDF) based polymer.

26. The method of claim 25, wherein the PVDF-based polymer is a modified PVDF-based polymer.

27. The method of claim 26, wherein the modified PVDF-based polymer is modified PVDF, modified polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-CTFE) or modified polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP).

28. The method of claim 1, wherein the polymer compound is cellulose.

29. The method of claim 28, wherein the cellulose is a modified cellulose.

30. The method of claim 1, wherein the polymer compound is an unsaturated polyester resin (UPR).

31. The method of claim 30, wherein the UPR is made from maleic anhydride and butanediol.

32. A single ion conducting polymer having formula A: Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; and M + It is a monovalent cation.

33. A single ion conducting polymer having formula B: Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + is a monovalent cation; and Where 3≤n≤50.

34. A single ion conducting polymer having formula C: Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + is a monovalent cation; and Where 5≤n≤500.

35. A single ion conducting polymer having formula D: Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + It is a monovalent cation; 1≤m≤500； 1≤n≤500; and 2≤m+n≤1000.

36. A single ion conducting polymer having formula E: Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + It is a monovalent cation; 1≤m≤500； 1≤n≤500； 1≤l≤500, and 3≤m+n+l≤1500.

37. A single ion conducting polymer having formula F: Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + is a monovalent cation; and 5≤n≤500。 38. A single ion conducting polymer having formula G: Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + is a monovalent cation; and 5≤n≤500。 39. A single ion conducting polymer having formula H: Wherein R is H or CH3; 1≤m≤6000； 0≤n≤1500； Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; and M + It is a monovalent cation.

40. A single ion conducting polymer having formula I: Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + It is a monovalent cation; 10≤m≤3000; and 50≤n≤6000。 41. A single ion conducting polymer having Formula J: Where R is H + , allyl or a combination thereof, and at least one R is Where R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + is a monovalent cation; and Where 100≤n≤6000.

42. A single ion conducting polymer having formula K: Wherein R is a linear C2-C6 alkyl group or a branched C3-C6 alkyl group, R f F; CF3; CF2CF3; (CF2) n CF3, wherein n≥1; C6F5; branched C3-C4 fluoroalkyl; linear perfluoroethyl ether, such as -(CF2CF2O) m -CF2CF3, where m = 1, 2 or 3; -(CF2O) p / (CF2CF2O) q -CF2CF3, wherein 1≤p≤10, 1≤q≤10, and the (CF2O) unit and the (CF2CF2O) unit are randomly copolymerized; or an aromatic group substituted with at least one fluorine and at least one electron withdrawing group; M + is a monovalent cation; and 5≤n≤100。 43. A single ion conducting polymer having the formula: Where 3≤n≤50; Where 5≤n≤500; Where 1≤m≤500, 1≤n≤500; and 2≤m+n≤1000; Where 1≤m≤500, 1≤n≤500, 1≤l≤500, and 3≤m+n+l≤1500; Where 5≤n≤500; Where 5≤n≤500; Wherein R=CH3, 1≤m≤6000, and 0≤n≤1500; Where 10≤m≤3000; and 50≤n≤6000; Where R is: H + , allyl or a combination thereof, and at least one R is and where 100≤n≤6000; or Where 5≤n≤100.

44. A single ion conducting electrolyte comprising a single ion conducting polymer as defined in any one of claims 32 to 43.

45. A single ion conducting cathode comprising a single ion conducting polymer as defined in any one of claims 32 to 43.

46. ​​A single ion conducting anode comprising a single ion conducting polymer as defined in any one of claims 32 to 43.

47. A solid-state battery comprising a positive electrode, a negative electrode and the single-ion conducting electrolyte according to claim 44.

48. A solid-state battery comprising the cathode according to claim 45, a negative electrode and an electrolyte.

49. A solid-state battery comprising a positive electrode, a negative electrode according to claim 46 and an electrolyte.

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