Multifunctional thiol conductor compound and preparation method thereof

Abstract

The present technology relates to multifunctional thiol conductor compounds that can be grafted to polymers and methods of making the same. In certain embodiments, the compounds of the present technology can be grafted onto polymers having low Tg to synthesize single ion conductive polymer electrolytes having improved conductivity. The multi-functional thiol conductor compounds of the present technology generally comprise: more than one sulfonamide anion covalently attached to a substitutable core (A) via a sulfide bond; a thiol functional group; and optionally a hydrocarbon side chain (L) attached to the substitutable core (A).

Description

Technical Field

[0001] The present technology generally relates to single ion polymer electrolytes, and in particular to multifunctionalized thiol conductor compounds and methods for preparing 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 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 a concentration gradient across the electrolyte and, therefore, dendrite formation.

[0004] Currently, existing routes to synthesize single-ion polymer electrolytes include the synthesis of lithium poly(ethylene oxide) methacrylic acid sulfonyl (trifluoromethylsulfonyl) imide (PEOMA-TFSI-Li) via copper-catalyzed alkyne-azide "click chemistry" cycloaddition. + ) monomer, as shown in Figure 1.

[0005] 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.

[0006] Alternatively, existing functionalized LiTFSI monomers, such as mono-TFSI thiol compounds, provide limited ion concentration increases after grafting onto polymers, especially when C=C bonds are scarce or inaccessible in the grafted polymer.

[0007]

[0006] Therefore, there is a need for alternative or improved functionalized TFSI monomers that overcome or reduce at least some of the problems discussed above. Summary of the invention

[0008] 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.

[0009] According to a broad aspect, the present technology relates to multifunctionalized thiol conductor compounds. In certain embodiments, the multifunctionalized thiol conductor compounds contain one or more thiol functional groups, which allow the multifunctionalized thiol conductor compounds to be easily grafted onto polymers, optionally with low Tg, to synthesize single ion conducting polymer electrolytes (SIPEs) with improved conductivity.

[0010] According to one aspect, a multifunctional thiol conductor compound is provided having Formula I:

[0011]

[0012] in:

[0013] A is a replaceable core;

[0014] L is absent or present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide, fluorinated ethylene oxide, cycloalkyl, fluorinated cycloalkyl, phenyl, or fluorinated phenyl;

[0015] Rf F; CF 3 CF 2 CF 3 ; (CH 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 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;

[0016] M + It is a monovalent cation;

[0017] L 1 is absent or is present, and when present is an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an oxyethylene group, a fluorinated oxyethylene group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group;

[0018] L 2 is absent or is present, and when present is an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an oxyethylene group, a fluorinated oxyethylene group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group;

[0019] L 3 is absent or is present, and when present is an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an oxyethylene group, a fluorinated oxyethylene group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group;

[0020] L 4 is absent or is present, and when present is an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an oxyethylene group, a fluorinated oxyethylene group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group;

[0021] R 1is absent or is present, and when present is an ether, thioether, ester, amide, carbamate derivative, urea, secondary amine, or tertiary amine;

[0022] R 2 is absent or is present, and when present is an ether, thioether, ester, amide, carbamate derivative, urea, secondary amine, or tertiary amine; and

[0023] n>1.

[0024] According to another aspect, a method for synthesizing a polyfunctional thiol conductor compound of the present invention is provided, the method comprising reacting a polyfunctional thiol compound with a lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-monomer having C=C in its backbone.

[0025] According to another aspect, a single ion conducting polymer electrolyte comprising the multifunctional thiol conductor compound of the present technology is provided.

[0026] According to another aspect, a single ion conducting polymer cathode comprising a multifunctional thiol conductor compound of the present technology is provided.

[0027] According to another aspect, a single ion conducting polymer anode comprising a multifunctional thiol conductor compound of the present technology is provided.

[0028] According to another aspect, a solid-state battery is provided that includes a positive electrode, a negative electrode, and the single-ion conductive polymer electrolyte of the present technology.

[0029] According to another aspect, a solid-state battery is provided that includes a single ion conducting polymer cathode of the present technology, a negative electrode, and an electrolyte.

[0030] According to another aspect, a solid-state battery is provided that includes a positive electrode, a single ion conducting polymer anode of the present technology, and an electrolyte.

[0031] According to another aspect, the multifunctionalized thiol conductor compounds of the present technology can be grafted onto different polymers.

[0032] According to another aspect, when the grafting density is the same, the multifunctional thiol conductor compounds of the present technology can increase the ion concentration on the polymer to which they are grafted compared to the monothiol TFSI compounds. This is particularly useful when the available C=C bonds on the polymer are scarce or inaccessible.

[0033] According to another aspect, the methods of the present technology are easy and do not require heating. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Reference will now be made to the drawings.

[0035] FIG. 1 shows the synthesis of poly(ethylene oxide) methacrylic acid sulfonyl (trifluoromethylsulfonyl) imide lithium (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). + ) existing synthetic routes; and

[0036] Figure 2 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

[0037] limited

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] As used herein, the expression "multifunctional thiol compound" refers to a thiol compound having more than two thiol groups in one molecule. Therefore, in the method of the present technology, such a multifunctional thiol compound can react with more than one LiTFSI-monomer having C=C in its main chain and have more than one LiTFSI-monomer attached thereto.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] In general, the present technology relates to multifunctionalized thiol conductor compounds 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 multifunctionalized thiol conductors with such polymers includes a thiol-ene "click" reaction, which can be used to produce single ion conducting polymer electrolytes (SIPEs) with low Tg. As a result, SIPEs containing the multifunctionalized thiol conductors of the present technology have higher conductivity than SIPEs obtained by polymerization of LITFSI-containing monomers having a styrene, acrylate, or methacrylate backbone.

[0047] In certain embodiments, the multifunctional thiol conductor compounds of the present technology include more than one sulfonamide anion covalently attached to a substitutable core (A) via a sulfide bond. The multifunctional thiol conductor compound also includes a thiol functional group and a hydrocarbon side chain (L) optionally attached to the substitutable core (A). The multifunctional thiol conductor compound may also include 0 to 4 hydrocarbon chains as linking groups (L). 1 To L 4 ) and 0 to 2 functional groups (R 1 and R 2 ); which connects the thiol group and / or the sulfonamide anion to the substitutable core (A).

[0048] In some embodiments, the multifunctional thiol conductor compound has Formula I:

[0049]

[0050] A is a substitutable core capable of accepting at least n+1 substituents, where n is an integer representing the number of sulfonamide anions attached to A. In some embodiments, A is capable of accepting n+1 substituents. In other embodiments, A is capable of accepting n+2 substituents.

[0051] In certain embodiments, n>1. In some embodiments, n is 2, 3, or 5. In other embodiments, n is 2. In yet other embodiments, n is 3. In yet other embodiments, n is 5.

[0052] In certain embodiments, the substitutable nucleus A is a boron atom, an aluminum atom, a carbon atom, or a silicon atom. In some embodiments, A is carbon. In other embodiments, A is

[0053] In certain embodiments, L may be absent or present, depending on the substitutability of A and the value of n (i.e., the sulfonamide anion attached to A). When present, L may be an n-alkyl, a fluorinated alkyl, a branched alkyl, an oxyethylene group, a fluorinated oxyethylene group, a cycloalkyl, a fluorinated cycloalkyl, a phenyl, or a fluorinated phenyl. In some embodiments, L is absent. In other embodiments, L is an n-alkyl, and n is 1, 2, 3, 4, 5, or 6. In other embodiments, L is -CH 2 CH 3 .

[0054] In certain embodiments, R f F; CF3; CF 2 CF 3 ; (CH 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-(CF 3 ) 2,-CF(CF 3 )-CF 2 -CF 3 and CF 2 -CF-(CF 3 ) 2 In other embodiments, the electron withdrawing group is -CN, -NO 2 , -CF 3 or -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 .

[0055] The M in the multifunctional thiol conductor compound of the present technology + 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 + .

[0056] As described above, L in the multifunctional thiol conductor compound of the present technology 1 , L 2 , L 3 and L 4 is a linking group that connects the thiol group and / or the sulfonamide anion to the substitutable core (A).

[0057] In certain embodiments, L 1 In some other embodiments, L 1 exists. When it exists, L 1 It can be an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an ethylene oxide group, a fluorinated ethylene oxide group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group. In some other embodiments, L 1 is n-alkyl, and n is 1, 2, 3, 4, 5 or 6. In other embodiments, L 1 For –CH 2 -.

[0058] L 2 It can also be absent or present. When present, L 2 It can be an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an ethylene oxide group, a fluorinated ethylene oxide group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group. In some embodiments, L 2 Does not exist.

[0059] L 3 It can also be absent or present. When present, L 3 It can be an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an oxyethylene group, a fluorinated oxyethylene group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group. In some embodiments, L 3 is n-alkyl, and n is 2, 3, 4, 5 or 6. In other embodiments, L 3 for (CH 2 ) 2 In some embodiments, L 3 Does not exist.

[0060] L 4 It can also be absent or present. When present, L 4 It can be an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an oxyethylene group, a fluorinated oxyethylene group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group. In some embodiments, L 4 Does not exist.

[0061] R in multifunctional thiol conductor compounds 1 and R 2 is a functional group which may or may not be present. When present, R 1 and R 2 Each of R and R is independently an ether, a thioether, an ester, an amide, a carbamic acid derivative, a urea, a secondary amine or a tertiary amine. 1 In some other embodiments, R 2 In some other embodiments, R 1 and R 2 Both are esters.

[0062] In one embodiment, R f For CF 3 ;M + For Li + ; L, L 1、 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 CF3 ;M + For Li + ; L is -CH 2 CH 3 ; L 1 For –CH 2 -;L 3 for (CH 2 ) 2 ; L 2 Does not exist; L 4 Does not exist; R 1 is an ester; and R 2 For esters.

[0063] In certain embodiments, the multifunctional thiol conductor compound has Formula II:

[0064]

[0065] Where R f 、M + , L 1 , L 2 , L 3 , L 4 , R 1 and R 2 The same as in formula I, A is a boron atom, an aluminum atom, as well as

[0066] L does not exist.

[0067] In certain embodiments of these embodiments, A is a boron atom or an aluminum atom. In other embodiments, A is a boron atom or an aluminum atom; R f For CF 3 ;M + For Li + ; L 1 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 some other embodiments, R f For CF 3 ;M + For Li + ; L 1 For –CH 2 -;L 3 for (CH 2 ) 2 ; L 2 Does not exist; L 4 Does not exist; R 1 is an ester; and R 2 For esters.

[0068] In certain embodiments, the multifunctional thiol conductor compound has Formula II:

[0069]

[0070] Where R f 、M + ,L,L 1 , L 2 , L 3 , L 4 , R 1 and R 2 Having the same definitions as in Formula I, A is a silicon atom or a carbon atom, and L is present.

[0071] In certain of these embodiments, A is carbon. In other embodiments, L is n-alkyl, and n is 1, 2, 3, 4, 5, or 6.

[0072] In yet other embodiments, A is carbon; L is n-alkyl, and n is 1, 2, 3, 4, 5, or 6; R f For CF 3 ;M + For Li + ; L 1 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 For esters.

[0073] In yet other embodiments, A is carbon; L is -CH 2 CH 3 ; R f For CF 3 ;M + For Li + ; L 1 For –CH 2 -;L 3 for (CH 2 ) 2 ; L 2 Does not exist; L 4 Does not exist; R 1 is an ester; and R 2 For esters.

[0074] In certain embodiments, the multifunctional thiol conductor compound has Formula III:

[0075]

[0076]

[0077] Where Rf 、M + , L 1 , L 2 , L 3 , L 4 , R 1 and R 2 has the same definitions as in Formula I; A is a carbon atom or a silicon atom; and L is absent.

[0078] In certain of these embodiments, A is carbon. In other embodiments, A is carbon; R f For CF 3 ;M + For Li + ; L 1 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 some other embodiments, A is carbon; R f For CF 3 ;M + For Li + ; L 1 For –CH 2 -;L 2 Does not exist; L 3 for (CH 2 ) 2 ; L 4 Does not exist; R 1 is an ester; and R 2 For esters.

[0079] In certain embodiments, the multifunctional thiol conductor compound has Formula IV:

[0080]

[0081] Where R f 、M + , L 1 , L 2 , L 3 , L 4 , R 1 and R 2 Having the same definition as in formula I;

[0082] A is dipentaerythritol nucleus L is absent; and n=5.

[0083] In certain embodiments of these embodiments, R f For CF 3 ;M + For Li + ; L1 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 For esters.

[0084] In some embodiments, R f For CF 3 ;M + For Li + ; L 1 For –CH 2 -;L 2 Does not exist; L 3 for (CH 2 ) 2 ; L 4 Does not exist; R 1 is an ester; and R 2 For esters.

[0085] In certain embodiments, the multifunctional thiol conductor compound has Formula V or Formula VI:

[0086]

[0087]

[0088] Where R is

[0089] In other embodiments, the multifunctionalized thiol conductor compound has Formula V. In still other embodiments, the multifunctionalized thiol conductor compound has Formula VI.

[0090] According to another aspect, the present technology relates to a method for synthesizing a multifunctional thiol conductor compound disclosed herein. In certain embodiments, the method of the present technology comprises reacting a multifunctional 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 a multifunctional thiol compound to a LiTFSI-monomer in the method of the present technology provides an easier synthetic route than a thiol-functionalized LiTFSI-monomer in which the thiol is directly attached to the LiTFSI via an alkyl chain.

[0091] In certain embodiments, the reaction of a multifunctional 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 a reaction also allows the generation of a variety of new polymer structures while enabling good spatial and temporal control of the material.

[0092] 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 sulfonamide anion is at the other (opposite) end of the LiTFSI-monomer. In other embodiments, the LiTFSI-monomer has the following formula VII, formula VIII, formula IX, formula X, or formula XI:

[0093]

[0094]

[0095] In certain embodiments, the multifunctional thiol compound is pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate and dipentaerythritol hexakis (3-mercaptopropionate). In some embodiments, the thiol compound is trimethylolpropane tris (3-mercaptopropionate). In other embodiments, the thiol compound is pentaerythritol tetrakis (3-mercaptopropionate).

[0096] In some embodiments, the method comprises reacting an excess of a thiol compound with a LiTFSI-monomer. In other embodiments, the method comprises reacting about 1 to about 4 equivalents of a thiol compound with a LiTFSI-monomer. In still other embodiments, the method comprises reacting about 1 to about 2 equivalents, or about 1 to about 3 equivalents of a multifunctional thiol compound with a LiTFSI-monomer.

[0097] In certain embodiments, the method of the present technology includes reacting a multifunctional thiol compound with a 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 a multifunctional thiol compound with a 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 other embodiments, a multifunctional thiol compound is reacted with a LiTFSI-monomer in THF.

[0098] In certain embodiments, reacting the multifunctional thiol compound with the LiTFSI-monomer comprises dissolving the multifunctional thiol compound and the LiTFSI-monomer together in a solvent. In other embodiments, reacting the multifunctional thiol compound with the LiTFSI-monomer comprises dissolving the multifunctional 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 multifunctional 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.

[0099] 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 multifunctional 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 multifunctional 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 multifunctional thiol compound with a LiTFSI-monomer at a temperature of about 25°C (RT).

[0100] In certain embodiments, the method of the present technology includes adding a catalyst to the reaction of a multifunctional thiol compound and a LiTFSI-monomer. 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 triethylamine (Et3N), diethylamine, di-n-propylamine, C2-C6 primary amines, N,N,N',N'-tetramethyl-1,8-naphthalenediamine, 1,8-diazabicyclo [5.4.0] 11 carbon-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), tripropyl phosphine, dimethylphenylphosphine, diphenylmethylphosphine, or triphenylphosphine.

[0101] In other embodiments, the catalyst is added in an amount of about 0.05 mol % to about 30 mol %.

[0102] In other embodiments, the method of the present technology includes adding a free radical initiator to the reaction of a multifunctional thiol compound with a 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. 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 multifunctional thiol conductor compounds, free radical initiators can be used to generate thiol radicals from multifunctional thiol compounds and / or complete the reaction between multifunctional thiol compounds and LiTFSI-monomers. 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). In still other embodiments, the free radical initiator is DMPA.

[0103] In other embodiments, the free radical initiator is added in an amount of about 0.01 mol% to about 5.0 mol%, about 0.01 mol% to about 2.0 mol%, about 0.01 mol% to about 1.0 mol%, about 0.01 mol% to about 0.5 mol%, about 0.01 mol% to about 0.25 mol%, about 0.01 mol% to about 0.1 mol%, or about 0.01 mol% to about 0.05 mol%.

[0104] 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 35 minutes. In some other embodiments, the free radical initiator is DMPA, which is added in an amount of about 0.01mol% to about 5mol% 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 0.01mol% to about 5mol%, and irradiated with UV light for a duration of about 30 minutes with a wavelength of about 365nm.

[0105] In certain embodiments, a catalyst, a free radical initiator, or a combination thereof may be added to the reaction of the multifunctional thiol compound and the LiTFSI-monomer in the step of dissolving the multifunctional 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 multifunctional thiol compound in the first solvent and dissolving the LiTFSI-monomer in the second solvent, or in the step of dissolving the multifunctional thiol compound and the LiTFSI-monomer together in the solvent. In some embodiments, a free radical initiator is added in the step of dissolving the multifunctional thiol compound and the LiTFSI-monomer together in the solvent.

[0106] Advantageously, the methods of the present technology produce products that can be easily purified and separated. Therefore, in certain embodiments, the methods of the present technology further include precipitating the multifunctional thiol conductor compound. In some embodiments, the precipitation of the multifunctional thiol conductor compound is carried out in dichloromethane (DCM), hexane, pentane, cyclohexane, octane or diethyl ether. In other embodiments, the precipitation of the multifunctional thiol conductor compound is carried out in DCM. Advantageously, the multifunctional thiol compound used in the methods of the present technology is soluble in such a solvent, thereby allowing excess multifunctional thiol compound to be substantially removed in the precipitation step.

[0107] In certain embodiments, the mass yield of multifunctionalized thiol conductor compounds obtained by the methods of the present technology is about 50% to about 99%, about 60% to about 80%, about 60% to about 70%, or about 65%.

[0108] 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 2 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 multifunctional thiol conductor compound of the present technology can be integrated in the anode film 14, the solid electrolyte 16, or the cathode film 18.

[0109] In some embodiments, the lithium salt contained in the solid electrolyte 16 may be LiCF 3 SO3 、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 、LiClO 4 、LiSCN、LiAsF 6 or LiBF 4 .

[0110] 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.).

[0111] Example

[0112] 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.

[0113] Example 1: Synthesis of a multifunctional thiol conductor compound according to one embodiment of the present technology

[0114] Pentaerythritol tetrakis (3-mercaptopropionate) (Sigma-Aldrich, 95%, 0.49 g, 1.0 mmol), 1-[3-(acryloyloxy)-propylsulfonyl]-1-(trifluoromethylsulfonyl)imide lithium (Formula VII, 1.0 g, 3.0 mmol) and 2,2-dimethoxy-2-phenylacetophenone (DMPA, 3 mg, 0.01 mmol) were mixed and dissolved in 3 mL of anhydrous THF. The solution was purged with Ar for 20 minutes and irradiated with 365 nm UV light (VWR hand lamp) for 35 minutes. After the reaction, the solution was precipitated into 20 mL of DCM to remove unreacted starting materials. The viscous transparent precipitate was collected and vacuum dried at 60° C. for about 20 hours, and 0.96 g of a transparent hard solid product was obtained. (Yield 64%). The content and purity of the final product were determined by 1 H NMR integration confirmed (DMSO-d6, ppm): 1.97 (-CH 2 -CH 2 -SO 2 -,p),2.42(-SH,m),2.57-2.74(-(CH 2 ) 2 -S-(CH 2 ) 2 -,m),3.02(-CH 2 -SO 2 -,t),4.03-4.17(-COO-CH 2 -CH 2 -CH 2 -SO 2 - and C-(CH 2 COO 4 -,m)).

[0115] A synthetic route for preparing a multifunctional thiol conductor compound according to this embodiment is presented below:

[0116]

[0117] Example 2: Synthesis of a multifunctional thiol conductor compound according to another embodiment of the present technology

[0118] A synthetic route for preparing a multifunctional thiol conductor compound according to this embodiment is presented below:

[0119]

[0120] 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 changes are determinable by those skilled in the art and may be performed without departing from the scope of information disclosed herein.

[0121] 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.

[0122] 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 multifunctional thiol conductor compound having formula I: in: A is a replaceable core; L is absent or present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide, fluorinated ethylene oxide, cycloalkyl, fluorinated cycloalkyl, phenyl, or fluorinated phenyl; R f F; CF 3； CF2CF3; (CH2) 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 absent or present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide, fluorinated ethylene oxide, cycloalkyl, fluorinated cycloalkyl, phenyl, or fluorinated phenyl; L2 is absent or present, and when present is an n-alkyl group, a fluorinated alkyl group, a branched alkyl group, an ethylene oxide group, a fluorinated ethylene oxide group, a cycloalkyl group, a fluorinated cycloalkyl group, a phenyl group, or a fluorinated phenyl group; L3 is absent or present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide, fluorinated ethylene oxide, cycloalkyl, fluorinated cycloalkyl, phenyl, or fluorinated phenyl; L4 is absent or present, and when present is n-alkyl, fluorinated alkyl, branched alkyl, ethylene oxide, fluorinated ethylene oxide, cycloalkyl, fluorinated cycloalkyl, phenyl, or fluorinated phenyl; R1 is absent or present, and when present is an ether, thioether, ester, amide, carbamate derivative, urea, secondary amine, or tertiary amine; R2 is absent or present, and when present is an ether, a thioether, an ester, an amide, a carbamate derivative, a urea, a secondary amine, or a tertiary amine; and n>1。 2 . The multifunctional thiol conductor compound according to claim 1 , wherein A is a boron atom, an aluminum atom, a carbon atom, or a silicon atom.

3. The multifunctional thiol conductor compound according to claim 2, wherein A is a carbon atom.

4. The multifunctional thiol conductor compound according to claim 1, wherein A is: 5 . The multifunctional thiol conductor compound according to claim 1 , wherein n is 2, 3 or 5.

6. The multifunctional thiol conductor compound according to any one of claims 1 to 5, wherein L is absent.

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

8. The multifunctional thiol conductor compound according to claim 7, wherein L is -CH2CH3.

9. The multifunctional thiol conductor compound according to any one of claims 1 to 8, wherein R f It is CF3.

10. The multifunctional thiol conductor compound according to any one of claims 1 to 8, wherein the electron withdrawing group is -CN, -NO2, -CF3, or -SO2CF3.

11. The multifunctional thiol conductor compound according to any one of claims 1 to 10, wherein the monovalent cation is an alkali metal cation.

12. The multifunctional thiol conductor compound according to claim 11, wherein the alkali metal cation is H + , K + 、Na + , Li + , Rb + , or Cs + .

13. The multifunctional thiol conductor compound according to claim 11 or claim 12, wherein the alkali metal cation is Li + .

14. The multifunctional thiol conductor compound according to any one of claims 1 to 13, wherein L1 is an n-alkyl group, and n is 1, 2, 3, 4, 5 or 6.

15. The multifunctional thiol conductor compound according to claim 14, wherein L1 is -CH2-.

16. The multifunctional thiol conductor compound according to any one of claims 1 to 15, wherein R1 is an ester.

17. The multifunctional thiol conductor compound according to any one of claims 1 to 16, wherein L2 is absent.

18. The multifunctional thiol conductor compound according to any one of claims 1 to 17, wherein L3 is an n-alkyl group, and n is 2, 3, 4, 5 or 6.

19. The multifunctional thiol conductor compound according to claim 18, wherein L3 is (CH2)2.

20. The multifunctional thiol conductor compound according to any one of claims 1 to 19, wherein R2 is an ester.

21. The multifunctional thiol conductor compound according to any one of claims 1 to 20, wherein L4 is absent.

22. The multifunctional thiol conductor compound according to claim 1 or 2, having formula II: Where A is a boron atom, an aluminum atom, as well as L does not exist.

23. The multifunctional thiol conductor compound according to claim 1 or 2, having formula II: wherein A is a carbon atom or a silicon atom; and L exists.

24. The multifunctional thiol conductor compound of claim 23, wherein A is carbon.

25. The multifunctional thiol conductor compound of claim 23 or 24, wherein L is an n-alkyl group, and n is 1, 2, 3, 4, 5 or 6.

26. The multifunctional thiol conductor compound of claim 25, wherein L is -CH2CH3.

27. The multifunctional thiol conductor compound according to claim 1 or 2, having formula III: wherein A is a carbon atom or a silicon atom; and L does not exist.

28. The multifunctional thiol conductor compound of claim 27, wherein A is carbon.

29. The multifunctional thiol conductor compound according to claim 1 or 2, having formula IV: Where A is a dipentaerythritol nucleus L does not exist; and n＝5。 30. The multifunctional thiol conductor compound according to claim 1 or 2, having formula V or formula VI: Where R is 31. A method for synthesizing a multifunctional thiol conductor compound according to any one of claims 1 to 30, comprising reacting a multifunctional thiol compound with a lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) monomer having C=C in its main chain.

32. The method according to claim 31, wherein the LiTFSI monomer compound has the formula VII, formula VIII, formula IX, formula X or formula XI:

33. The method according to claim 32, wherein the LiTFSI monomer compound is:

34. The method according to any one of claims 31 to 33, wherein the multifunctional thiol compound is pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, or dipentaerythritol hexa(3-mercaptopropionate).

35. The method of claim 34, wherein the thiol compound is trimethylolpropane tris(3-mercaptopropionate).

36. The method of claim 34, wherein the thiol compound is pentaerythritol tetrakis (3-mercaptopropionate).

37. A method according to any one of claims 31 to 36, wherein no heating step is required.

38. The method of any one of claims 31 to 37, further comprising precipitating the multifunctional thiol conductor compound.

39. A single ion conductive polymer electrolyte comprising the multifunctional thiol conductor compound according to any one of claims 1 to 30.

40. A single ion conducting polymer cathode comprising the multifunctional thiol conductor compound according to any one of claims 1 to 30.

41. A single ion conducting polymer anode comprising the multifunctional thiol conductor compound according to any one of claims 1 to 30.

42. A solid-state battery comprising a positive electrode, a negative electrode and the single-ion conductive polymer electrolyte according to claim 39.

43. A solid-state battery comprising the cathode according to claim 40, a negative electrode and an electrolyte.

44. A solid-state battery comprising a positive electrode, the anode according to claim 41 and an electrolyte.

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