Thiol-functionalized conductor compounds and methods of making same

Abstract

The present technology relates to thiol-functionalized conductors that can be grafted to polymers and methods of making the same. In certain embodiments, a thiol-functionalized conductor may be grafted to a polymer having a low Tg to synthesize a single ion conductive polymer electrolyte (SIPE) having improved conductivity. A thiol-functionalized conductor compound comprises: a sulfonyl imide anion covalently attached at one end, the sulfonyl imide 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.

Description

Technical Field

[0001] The present technology relates generally to single ion conducting polymer electrolytes and, in particular, to thiol functionalized conductor compounds and methods for making the same. Background Art

[0002] Lithium batteries using lithium metal as negative electrodes have excellent energy density. However, with repeated cycles, when the battery is recharged, such batteries may experience 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 effects of morphological evolution of the surface of the lithium metal anode, including dendrite growth, lithium metal batteries generally use a pressure system and a solid polymer electrolyte 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, thereby penetrating the solid polymer electrolyte and ultimately causing a "soft" short circuit between the negative electrode and the positive electrode, resulting in a decrease in battery performance or poor performance. Therefore, the growth of dendrites may still degrade the cycle characteristics of the battery and constitute 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 were found to lack conductivity and / or mechanical properties. However, single-ion conducting polymer electrolytes (SIPEs) have emerged as promising candidates because the transference number of lithium cations is close to one and thus prevents the formation of concentration gradients across the electrolyte, and the resulting dendrite formation.

[0004] Currently, the existing route to synthesize single-ion polymer electrolytes involves the synthesis of poly(ethylene oxide)methacrylic acid sulfonyl (trifluoromethylsulfonyl) imide lithium (PEOMA-TFSI–-Li+) monomers via copper-catalyzed alkyne-–azide “click chemistry” cycloaddition, as shown in Figure 1. However, the azide-clicked PEOMA-TFSI-–Li + The synthesis of is complex and not suitable for large-scale production for at least the following reasons: (1) the azide and alkyne functional groups must be provided on the precursors; (2) the intermediate molecules are expensive to make and are not commercially available; (3) alkali metal azide salts such as LiN 3 and NaN 3are hazardous and difficult to work with in large quantities, which hinders the scalability of the precursor; (4) the final polymer is a PEO-based polymer, which is not suitable for high voltage applications; and (5) in terms of functional group availability, the chemistry is not universal as there are few commercial polymers with internal triple bonds.

[0005] However, the inventors of the present technology have recently discovered new routes to synthesize single-ion polymer electrolytes that include synthesizing LiTFSI monomers at reduced cost and with high atom economy (i.e., generating minimal reactant waste), particularly due to including a single step and bypassing the synthesis of nitrogen-based organic cation intermediates. These new synthetic routes can be used to prepare SIPEs with styrene, acrylate, or methacrylate backbones. However, the resulting homopolymers derived from such LiTFSI monomers have high glass transition temperatures (Tg) and low room temperature conductivity, which hinder their performance as electrolytes and ultimately hinder the performance of batteries. In addition, such LiTFSI monomers do not contain functional groups suitable for grafting onto polymers with low Tg to help alleviate these deficiencies.

[0006]

[0006] Therefore, there is a need for alternative or improved methods of synthesizing SIPEs that contain various polymer backbones having low Tgs and that overcome or reduce at least some of the above-mentioned problems. Summary of the invention

[0007] According to a broad aspect, the present technology relates to thiol-functionalized conductors. In certain embodiments, thiol-functionalized conductors can be grafted onto polymers with low Tg to synthesize single ion conducting polymer electrolytes (SIPEs) with improved conductivity.

[0008] According to one aspect, there is provided a thiol-functionalized conductor compound having Formula I:

[0009]

[0010] in:

[0011] R f F; CF 3 CF 2 CF 3 ;(CF 2 ) n CF 3 , where n≥1; C 6 F 5 ; Branched C 3 -C 4 Fluoroalkyl; -(CF 2 CF 2 O) m -CF 2 CF3 , where m = 1, 2 or 3; -(CF 2 O) p / (CF 2 CF 2 O) q -CF 2 CF 3 , where 1≤p≤10, 1≤q≤10, and (CF 2 O) units and (CF 2 CF 2 O) units are randomly copolymerized; or aromatic groups substituted with at least one fluorine and at least one electron withdrawing group;

[0012] M + It is a monovalent cation;

[0013] L 1 is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide linking group, fluorinated ethylene oxide linking group, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl;

[0014] L 2 is absent or is present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, oxyethylene linking group, fluorinated oxyethylene linking group, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl;

[0015] L 3 is absent or is present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, oxyethylene linking group, fluorinated oxyethylene linking group, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl;

[0016] R 1 is an ether, thioether, ester, amide, carbamate, urea, secondary amine or tertiary amine; and

[0017] R 2 Absent or present, and when present is an ether, thioether, ester, amide, carbamate, urea, secondary amine or tertiary amine.

[0018] According to another aspect, a method for synthesizing a thiol-functionalized conductor compound of the present invention is provided, the method comprising reacting a thiol compound with a lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-monomer having C=C in its backbone.

[0019] According to another aspect, a single ion conducting polymer electrolyte is provided, which includes a thiol functionalized conductor compound of the present technology.

[0020] According to another aspect, a solid-state battery is provided that includes a positive electrode, a negative electrode, and a single-ion conducting polymer electrolyte including a thiol-functionalized conductor compound of the present technology.

[0021] According to another aspect, the thiol-functionalized conductor compounds of the present technology can be grafted onto different polymers.

[0022] According to another aspect, the method for synthesizing the thiol-functionalized conductor compound of the present technology is effective for inexpensive thiol compounds such as 1,3-propane-dithiol and 2,2'-(ethylenedioxy)diethanethiol, and thus provides an economical synthesis route for single-ion polymer electrolytes.

[0023] According to another aspect, the methods of the present technology are easy and do not require heating. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Reference will now be made to the drawings.

[0025] FIG1 shows an existing synthetic route for lithium poly(ethylene oxide) methacrylic acid sulfonyl(trifluoromethylsulfonyl)imide (PEOMA-TFSI-–Li+) using azide-alkyne click chemistry according to Sipei Li et al., ACS Energy Lett. 2018, 3, 1, 20–27 (incorporated herein by reference).

[0026] Figure 2 The thiol-functionalized conductor compound (bottom) according to one embodiment of the present technology is shown compared to the starting materials: LiTFSI-acrylate compound (top) and 1,3-propanedithiol (middle). 1 H-NMR spectrum.

[0027] Figure 3 Shows Figure 2 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'.

[0028] Figure 4 is a schematic diagram of a plurality of electrochemical cells forming a solid-state battery including a single-ion conductive polymer electrolyte of the present technology. DETAILED DESCRIPTION

[0029] definition

[0030] 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.

[0031] It must be noted that as used in the specification and the appended claims, unmodified nouns include plural referents unless the context clearly dictates otherwise.

[0032] As used herein, the term "and / or" should be deemed to specifically disclose each of the two specified features or components, either together or individually. For example, "A and / or B" should be deemed to specifically disclose each of (i) A, (ii) B, and (iii) A and B, just as if each were individually listed herein.

[0033] 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.

[0034] As used herein, the term "facile" refers to a chemical reaction that occurs easily.

[0035] As used herein, the term "processing" refers to the series of operations required to separate and purify the products of a chemical reaction.

[0036] As used herein, the term "substantially" means to a great or significant extent.

[0037] As used herein, the expression "click chemistry" or "click reaction" refers to a reaction that is simple; has high efficiency and high yield; and produces stereospecific and easily removable by-products. In addition, such reactions can be carried out in easily removable or benign solvents. Click chemistry was conceptualized by Sharpless et al., Angew. Chem. Int. Ed. 2001, 40, 2004-2021, which is incorporated herein by reference.

[0038] 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.

[0039] 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 carried out in a variety of ways. In addition, the wording and terminology used herein are for descriptive purposes and should not be considered restrictive.

[0040] Broadly, the present technology relates to thiol-functionalized conductors that can be grafted onto polymers, such as commercially available polymers, including but not limited to polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), and poly(acrylonitrile-co-butadiene). In some cases, the grafting reaction of the thiol-functionalized conductors with such polymers includes a thiol-ene "click" reaction that produces a single ion conducting polymer electrolyte (SIPE) with a low Tg. Thus, SIPEs containing thiol-functionalized conductors of the present technology have higher conductivity than SIPEs obtained by polymerization of LiTFSI-containing monomers having a styrene, acrylate, or methacrylate backbone.

[0041] In certain embodiments, the thiol-functionalized conductor compounds of the present technology comprise: a sulfonimide anion covalently attached at one end, the sulfonimide anion being associated with a monovalent cation; 1 to 3 hydrocarbon chains as linking groups (L); 1 to 2 functional groups (R); and a thiol group at the other end of the compound. In some embodiments, the thiol-functionalized conductor compound has Formula I:

[0042]

[0043] In certain embodiments, R f F; CF 3 CF 2 CF 3 ;(CF 2 ) n CF 3 , where n≥1; C 6 F 5 ; Branched C 3 -C 4 Fluoroalkyl; linear perfluoroethyl ether groups, such as -(CF 2 CF 2 O) m -CF 2 CF 3 , where m = 1, 2 or 3; -(CF 2 O) p / (CF 2 CF 2 O) q -CF 2 CF 3 , where 1≤p≤10, 1≤q≤10, and (CF 2 O) units and (CF 2 CF 2 O) units are randomly copolymerized; or aromatic groups substituted with at least one fluorine and at least one electron withdrawing group. In some embodiments, the branched C 3 -C 4 Fluoroalkyl groups include -CF-(CF3 ) 2 ,-CF(CF 3 )-CF 2 -CF 3 and CF 2 -CF-(CF 3 ) 2 In other embodiments, the electron withdrawing group is selected from -CN, -NO 2 , -CF 3 and-SO 2 CF 3 In other embodiments, the aryl compound substituted with at least one fluorine and at least one electron withdrawing group is -C 6 F 4 -CF 3 or -C 6 F 4 -SO 2 CF 3 In some further embodiments, R f For CF 3 .

[0044] 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 + .

[0045] L in thiol-functionalized conductor compounds 1 , L 2 and L 3 It is a linking group that connects at least the sulfonyl imide anion at one end of the compound to the thiol group at the other end.

[0046] In certain embodiments, L 1 is n-alkyl, fluorinated alkyl, branched alkyl, oxyethylene linker, fluorinated oxyethylene linker, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl. 1 is n-alkyl, and n is 1, 2, 3, 4, 5 or 6. In other embodiments, L 1 for (CH 2 ) 3 .

[0047] L 2It can be absent or present. When present, L 2 is n-alkyl, fluorinated alkyl, branched alkyl, oxyethylene linker, fluorinated oxyethylene linker, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl. 2 is n-alkyl, and n is 1, 2, 3, 4, 5 or 6. In other embodiments, L 2 for (CH 2 ) 2 .

[0048] L 3 It can also be absent or present. When present, L 3 is n-alkyl, fluorinated alkyl, branched alkyl, oxyethylene linker, fluorinated oxyethylene linker, cycloalkyl, fluorinated cycloalkyl, phenyl or fluorinated phenyl. 3 is n-alkyl, and n is 2, 3, 4, 5 or 6. In other embodiments, L 3 for (CH 2 ) 3 .

[0049] R in thiol-functionalized conductor compounds 1 and R 2 R is a functional group. 2 Can be absent or present. 1 and R 2 (when present) are each independently an ether, a thioether, an ester, an amide, a carbamate, a urea, a secondary amine, or a tertiary amine. 1 In some other embodiments, R 2 For thioether.

[0050] In one embodiment, R f For CF 3 , M + For Li + , L 1 , L 2 and L 3 Each is an n-alkyl group, wherein n is 2, 3, 4, 5 or 6, R 1 is an ester, and R 2 In another embodiment, R f For CF 3 , M + For Li + , L 1 and L 3 for (CH 2 ) 3 , L 2 for (CH 2 ) 2 , R1 is an ester, and R 2 For thioether.

[0051] In certain embodiments, thiol-functionalized conductor compounds of the present technology have Formula II or Formula III:

[0052]

[0053] According to another aspect, the present technology relates to a method for synthesizing the thiol-functionalized conductor compounds disclosed herein. In certain embodiments, the method of the present technology comprises reacting a thiol compound with a lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-monomer having C=C in its backbone. Advantageously, the method of the present technology comprises a single step. In addition, the direct addition of thiol to LiTFSI-monomer in the method of the present technology provides an easier synthetic route than thiol-functionalized LiTFSI-monomer in which the thiol is directly attached to LiTFSI via an alkyl chain.

[0054] In certain embodiments, the reaction of the thiol compound with a LiTFSI-monomer having C=C in its backbone is a thiol-ene "click" reaction. Advantageously, the thiol-ene click reaction is simple and efficient. Such reactions also allow the generation of a variety of new polymer structures while enabling good spatial and temporal control of the material.

[0055] In certain embodiments, the C=C in the LiTFSI-monomer is at one end of the molecule. In some embodiments, the C=C is at one end of the molecule 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:

[0056]

[0057]

[0058] In certain embodiments, the thiol compound is an n-alkyl dithiol, an ethylene glycol-based dithiol, a 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-(CH 2 ) r-SH, wherein r = 2, 3, 4, 5, 6, 8, 9, 11 or 16. In other embodiments, the ethylene glycol-based dithiols have the formula SH-(CH 2 CH 2 O) s -CH 2 CH 2 -SH, wherein s=2, 3 or 5. In yet 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 yet other embodiments, the thiol compound is 1,3-propane-dithiol. In yet 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 provide an economical way to synthesize SIPE.

[0059] In some embodiments, the method includes reacting an excess of the thiol compound with the LiTFSI-monomer. In other embodiments, the method includes reacting about 1 equivalent to about 4 equivalents of the thiol compound with the LiTFSI-monomer. In yet other embodiments, the method includes 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.

[0060] In certain embodiments, the method of the present technology includes reacting the thiol compound with the LiTFSI-monomer in bulk (i.e., without solvent). Such an embodiment is reasonable when the reactants are miscible with each other. In other embodiments, the method of the present technology includes reacting the thiol compound with 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 is reacted with the LiTFSI-monomer in THF.

[0061] In certain embodiments, reacting the thiol compound with the LiTFSI-monomer comprises dissolving the thiol compound and the LiTFSI-monomer together in a solvent. In other embodiments, reacting the thiol compound with 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.

[0062] In certain embodiments, the LiTFSI-monomer dissolved in the second solvent is added slowly and / or in a dropwise manner to the thiol compound dissolved in the first solvent. This prevents temperature jumps and solvent evaporation. However, the methods of the present technology are not limited to a specific order of adding reagents. 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 embodiments, the thiol compound dissolved in the first solvent can be added slowly and / or in a dropwise manner to the LiTFSI-monomer dissolved in the second solvent.

[0063] In certain embodiments, the methods of the present technology do not require a heating step. Specifically, in certain embodiments, the methods of the present technology include reacting a thiol compound with a LiTFSI-monomer at a temperature of about 15°C to about 30°C. In other embodiments, the method includes reacting a thiol compound with a 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 method includes reacting a thiol compound with a LiTFSI-monomer at a temperature of about 25°C (RT).

[0064] In other embodiments, the methods of the present technology include reacting the thiol compound with the LiTFSI-monomer for about 12 hours to about 24 hours. In other embodiments, the methods of the present technology include reacting the thiol compound with 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 methods of the present technology include reacting the thiol compound with the LiTFSI-monomer for at least about 12 hours.

[0065] In other embodiments, the method of the present technology 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 (Et 3 N), diethylamine, di-n-propylamine, C 2 -C 6 primary amine, N,N,N',N'-tetramethyl-1,8-naphthalenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), tripropylphosphine, dimethylphenylphosphine, diphenylmethylphosphine, or triphenylphosphine. In some embodiments, the catalyst is Et 3 N. In other embodiments, the catalyst is added in an amount of about 0.05 mol % to about 30 mol %.

[0066] In other embodiments, the method of the present technology 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 under mild conditions and promote free radical reactions. In the method of the present technology, the free radical initiator can be used to generate sulfur 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 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).

[0067] 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%.

[0068] In certain 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 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 irradiated with UV light for a duration of about 30 minutes with a wavelength of about 365nm.

[0069] In certain embodiments, 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 with the LiTFSI-monomer at the step of dissolving the thiol compound in the first solvent, dissolving the LiTFSI-monomer in the second solvent, at both the step of dissolving the thiol compound in the first solvent and dissolving the LiTFSI-monomer in the second solvent, or at the step of dissolving the thiol compound and the LiTFSI-monomer together in a solvent. In some embodiments, the catalyst is added at the step of dissolving the thiol compound in the first solvent. In other embodiments, the free radical initiator is added at the step of dissolving the thiol compound and the LiTFSI-monomer together in a solvent.

[0070] Advantageously, the methods of the present technology produce monosubstituted thiol-functionalized conductor compounds as their major products, such as by 1 H-NMR spectroscopy confirmed Figure 2 and Figure 3 ). The product can be easily processed to purify and isolate it. Therefore, in certain embodiments, the method of the present technology also includes 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 method of the present technology is soluble in such a solvent, thereby allowing the excess thiol compound to be substantially removed in the precipitation step.

[0071] In certain embodiments, the mass yield of thiol-functionalized conductor compounds obtained by the methods of the present technology is about 60% to about 99%, about 70% to about 90%, about 80% to about 90%, about 80% or about 85%.

[0072] According to 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 4 A 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 ionic 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 in the range of about 20 microns to about 100 microns. In other embodiments, the thickness of the solid electrolyte 16 is in the range of about 5 microns to about 50 microns. In other embodiments, the thickness of the positive electrode film 18 is in the range of about 20 microns to about 100 microns. The thiol-functionalized conductor compound of the present technology can be integrated in the anode film 14, the solid electrolyte 16, or the cathode film 18.

[0073] In some embodiments, the lithium salt contained in the solid electrolyte 16 may be LiCF 3 SO 3 、LiB(C 2 O 4 ) 2 、LiN(CF 3 SO 2 ) 2 、LiN(FSO 2 ) 2 、LiC(CF 3 SO 2 ) 3 、LiC(CH 3 )(CF 3 SO 2 ) 2 、LiCH(CF 3 SO 2 ) 2 、LiCH 2 (CF 3 SO 2 )、LiC 2 F 5 SO 3 、LiN(C 2 F 5 SO 2 ) 2 、LiN(CF 3 SO 2 )、LiB(CF 3 SO 2 ) 2 、LiPF 6 、LiSbF 6 、LiClO4 、LiSCN、LiAsF 6 or LiBF 4 .

[0074] The internal operating temperature of the battery 10 in the electrochemical cell 12 is generally 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 over a wide temperature range (about -40° C. to about +70° C.).

[0075] Example

[0076] 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.

[0077] Example 1: Synthesis of a thiol-functionalized single ion conductor according to one embodiment of the present technology

[0078] In brief, in an oven-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 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)imide lithium (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). After the reaction, THF was evaporated, and the crude product was precipitated four times in 200 mL of hexane to remove excess dithiol. The viscous liquid product was collected and dried on a rotary evaporator. About 3.7 g of a clear, light yellow viscous J517 was obtained (85% yield).

[0079] The synthetic route for preparing thiol-functionalized single ion conductors according to this embodiment is shown below:

[0080]

[0081] Example 2: Synthesis of a thiol-functionalized single ion conductor according to another embodiment of the present technology

[0082] 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.

[0083] The synthetic route for preparing thiol-functionalized single ion conductors according to this embodiment is shown below:

[0084]

[0085] Those skilled in the art will appreciate variations and modifications after reading this disclosure. The disclosed features may be implemented in any combination and sub-combination (including multiple subordinate combinations and sub-combinations) with one or more other features described herein. Each feature described or illustrated above (including any component thereof) may be combined or integrated in other systems. In addition, certain features may be omitted or not implemented. Examples of variations, substitutions, and alterations are determinable by those skilled in the art and may be performed without departing from the scope of information disclosed herein.

[0086] It will 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.

[0087] All references cited in this specification and their references are incorporated herein by reference in their entirety to the extent applicable for teachings of additional or alternative details, features and / or technical background.

Claims

1. A thiol-functionalized conductor compound having 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, fluorinated 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, fluorinated 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, oxyethylene linking group, fluorinated oxyethylene 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.

2. The thiol-functionalized conductor compound according to claim 1, wherein R f It is CF3.

3. The thiol-functionalized conductor compound of claim 1, wherein the electron withdrawing group is -CN, -NO2, -CF3 or -SO2CF3.

4. The thiol-functionalized conductor compound of claim 1, wherein the monovalent cation is an alkali metal cation.

5. The thiol-functionalized conductor compound of claim 4, wherein the alkali metal cation is H + , K + 、Na + , Li + , Rb + or Cs + .

6. The thiol-functionalized conductor compound according to claim 4 or claim 5, wherein the alkali metal cation is Li + .

7. The thiol-functionalized conductor compound according to any one of claims 1 to 6, wherein L1 is an n-alkyl group, and n is 1, 2, 3, 4, 5 or 6.

8. The thiol-functionalized conductor compound of claim 7, wherein L1 is (CH2)3.

9. The thiol-functionalized conductor compound according to any one of claims 1 to 8, wherein L2 is an n-alkyl group, and n is 1, 2, 3, 4, 5 or 6.

10. The thiol-functionalized conductor compound of claim 9, wherein L2 is (CH2)2.

11. The thiol-functionalized single ion conductor compound according to any one of claims 1 to 10, wherein L3 is an n-alkyl group, and n is 2, 3, 4, 5 or 6.

12. The thiol-functionalized conductor compound of claim 11, wherein L3 is (CH2)3.

13. The thiol-functionalized conductor compound according to any one of claims 1 to 12, wherein R1 is an ester.

14. A thiol-functional conductor compound according to any one of claims 1 to 13, wherein R2 is a thioether.

15. The thiol-functionalized conductor compound according to any one of claims 1 to 14, having formula II or formula III:

16. A method for synthesizing a thiol-functionalized conductor compound according to claim 1, comprising reacting a thiol compound with a lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) monomer having C=C in its backbone.

17. The method according to claim 16, wherein the LiTFSI monomer compound has the following formula IV, formula V, formula VI, formula VII or formula VIII:

18. The method according to claim 16, wherein the thiol compound is 1,3-propane-dithiol.

19. The method according to claim 16, wherein the thiol compound is 2,2'-(ethylenedioxy)diethanethiol.

20. A method according to any one of claims 16 to 19 wherein no heating step is required.

21. The method of any one of claims 16 to 20, further comprising precipitating the thiol-functionalized conductor compound.

22. A single ion conducting polymer electrolyte comprising the thiol functionalized conductor compound according to any one of claims 1 to 15.

23. A single ion conducting polymer cathode comprising the thiol functionalized conductor compound according to any one of claims 1 to 15.

24. A single ion conducting polymer anode comprising the thiol functionalized conductor compound according to any one of claims 1 to 15.

25. A solid-state battery comprising a positive electrode, a negative electrode and the single-ion conductive polymer electrolyte according to claim 22.

26. A solid-state battery comprising the cathode according to claim 23, a negative electrode and an electrolyte.

27. A solid-state battery comprising a positive electrode, the anode according to claim 24 and an electrolyte.

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