Compound

Abstract

A compound of formula (I), wherein X is Al or B, and R 1 is, independently in each occurrence, a substituent; and two R 1 The groups may be linked to form a ring, M + is a cation. The compound may be used in a metal ion battery or a metal battery. [Formula 1] TIFF2024519014000023.tif34134

Description

[Technical field]

[0001] CN101771166 discloses ionic liquid electrolytes composed of specific organic lithium borate or lithium aluminate compounds and specific organic compounds containing amide functional groups.

[0002] JP2004 / 265785 discloses an electrolyte material of formula (I). [ka]

[0003] JP2006 / 107793 discloses ions having a fluorinated alkoxy group coordinated to a metal element.

[0004] JP03409852 discloses compounds of the following formula: [ka] No. 8,394,539 discloses lithium salts having a fluorinated chelating orthoborate anion for use as electrolytes or electrolyte additives in lithium ion batteries. The lithium salts have two chelate rings formed by the coordination of two bidentate ligands to a single boron atom.

[0005] E. Zygadó-Monikowska et al, “Lithium conducting ionic liquids based on lithium borate salts”, Journal of Power Sources 195 (2010) 6055-6061, discloses the reaction of trialkoxyborates with butyllithium to form Li{[CH3(OCH2CH2)nO]3BC4H9}.

[0006] Michael Rohde et al, “Li[B(OCH2CF3)4]: Synthesis, Characterization and Electrochemical Application as a Conducting Salt for LiSB Batteries”, ChemPhysChem 2015,16,666-675, discloses the reaction of lithium borohydride with an excess of 2,2,2-trifluorethanol to form Li[B(OCH2CF3)4].

[0007] R Tao et al, “Enhancement of ionic conductivity by mixing lithium borate with lithium aluminate” discloses a compound of the following formula: [ka]

[0008] Andreas Thum et al., “Solvate ionic liquids based on lithium bis(trifluoromethanesulfonyl)imide-glyme systems: coordination in MD simulations with scaled charges” Phys. Chem. Chem. Phys., 2020, 22, 525-535, disclose equimolar mixtures of lithium bis(trifluoromethanesulfonyl)imide (Li[NTf2]) with triglyme or tetraglyme.

[0009] Daniel J. Eyckens and Luke C. Henderson, “A Review of Solvate Ionic Liquids: Physical Parameters and Synthetic Applications”, Frontiers in Chemistry, April 2019, Vol 7, Article 263, is a review of solvate ionic liquids.

[0010] Seki, S., Takei, K., Miyashiro, H., and Watanabe, M “Physicochemical and electrochemical properties of glyme-LiN(SO2F)2 complex for safe lithium ion secondary battery electrolyte”, J. Electrochem. Soc. 158, A769-A774 (2011) discloses the electrolyte performance of a 1:1 molar mixture of CH3-(OC2H4)3-CH3(TG) / LiN(SO2F)2(LiFSI) for lithium ion secondary batteries. Summary of the Invention

[0011] In some embodiments, the disclosure provides a compound of formula (I): [ka] In the formula, X is Al or B, and R 1 is, independently in each occurrence, a substituent; and two R 1 The groups may be linked to form a ring, M + is a cation.

[0012] In some embodiments, R 1 According to these embodiments, optionally, each R 1 is independently 1-20It is an alkyl group, in which one or more non-adjacent C atoms of the alkyl group can be replaced by O, S, CO, or COO, and one or more H atoms of the alkyl group can be replaced by F.

[0013] Optionally, each R 1 are independently selected from alkyl groups and alkyl ether groups, and one or more H atoms may be replaced with F.

[0014] In some embodiments, each R 1 is the same.

[0015] In some embodiments, the compound of formula (I) comprises at least two different R 1 It contains a group.

[0016] In some embodiments, R of formula (I) 1 The groups are linked so that the compound of formula (I) has the formula (Ia): [ka] In the formula, R 2 is, in each occurrence, independently a divalent organic group.

[0017] Optionally, M of the compound of formula (I) + is an alkali metal ion, optionally a lithium ion.

[0018] Optionally, M + is a solvated cation.

[0019] Optionally, the solvent of the solvate is selected from solvents containing at least one ether group.

[0020] In some embodiments, the present disclosure provides a formulation comprising or consisting of a solvent and a compound of formula (I), the formulation comprising M + More preferably, the solvent contains 10 moles or less of solvent per mole of the solvent, more preferably 7 moles or less or 6 moles or less of solvent.

[0021] Some or all of the solvent present in the formulation may be a solvating solvent. The amount of solvating solvent in the compound of formula (I) corresponds to the solvent. 1 H NMR peaks and the -OR group 1 The compound after vacuum treatment to remove free (non-solvated) solvent was obtained by integrating the peaks corresponding to 1 It can be determined from the 1 H NMR spectrum.

[0022] In some embodiments, the present disclosure provides a method of forming a compound of formula (I), comprising reacting a compound of formula (II) with at least one compound selected from formulas (IIIa) and (IIIb). [ka]

[0023] Optionally, the compound of formula (IIIa) is selected from a monohydric alcohol and a monocarboxylic acid, and the compound of formula (IIIb) is selected from a diol and a dicarboxylic acid.

[0024] Optionally, M of the compound of formula (I) + is solvated and the reaction is carried out in a reaction mixture that contains a solvent of the solvate.

[0025] In some embodiments, the present disclosure provides a compound of formula (I) + The present invention provides a method of solvating a compound of formula (I) comprising at least partially replacing the solvent of the solvate with another solvent.

[0026] In some embodiments, the present disclosure provides a polymer comprising a repeat unit of formula (IV): [ka] where RG is a repeating group of the polymer and R 3 is a substituent, and X and M + However, as mentioned above.

[0027] In some embodiments, the present disclosure provides a metal or metal-ion battery comprising a negative electrode, a positive electrode, and a compound or polymer of formula (I) described herein disposed between the negative electrode and the positive electrode.

[0028] Optionally, the battery is a metal battery that includes an anode protection layer that includes a compound or polymer disposed between the anode and cathode. [Brief description of the drawings]

[0029] [Figure 1] FIG. 1 is a schematic diagram of a battery according to some embodiments of the present disclosure having a separator comprising a compound described herein. [Diagram 2] FIG. 1 is a schematic diagram of a battery according to some embodiments of the present disclosure having an anode protective layer comprising a compound described herein. [Diagram 3] 1 is an NMR spectrum of a compound according to one embodiment of the disclosure formed by reaction in THF. [Figure 4] 1 is an NMR spectrum of a compound according to one embodiment of the present disclosure formed by reaction in dimethoxyethane (DME). [Diagram 5] 5 is an NMR spectrum of the compound of FIG. 4 after the addition of various amounts of DME. [Figure 6] 5 is an NMR spectrum of the compound of FIG. 4 after the addition of various amounts of DME. [Figure 7] 5 is an NMR spectrum of the compound of FIG. 4 after the addition of various amounts of DME. [Figure 8] 5 is an NMR spectrum of the compound of FIG. 4 after the addition of various amounts of DME. [Figure 9] 5 is an NMR spectrum of the compound of FIG. 4 after the addition of various amounts of DME. [Figure 10] FIG. 4 is a cyclic voltammetry plot for the compound of FIG. 3, where the compound was disposed between a copper foil working electrode and a lithium foil counter electrode. [Figure 11] 11 is an image of lithium deposited on the copper foil described in FIG. 10. [Figure 12] 4 is a Nyquist plot of the compound of FIG. 3. [Figure 13] FIG. 10 is a Nyquist plot of the compounds of FIGS. 5 to 9. [Figure 14] 1 is a plot of ionic conductivity versus DME:Li cation ratio.

[0030] The drawings are not drawn to scale and have various perspectives and views. The drawings are of several implementations and examples. While the technology is susceptible to various modifications and alternative forms, specific embodiments are shown by way of example in the drawings and are described in detail below. However, it is not intended to limit the technology to the specific implementations described. On the contrary, the technology is intended to cover all modifications, equivalents, and alternatives falling within the scope of the technology as defined by the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] Unless the context clearly requires otherwise, throughout the description and claims, words such as "comprise", "comprising" and the like shall be interpreted in an inclusive sense, i.e., "including but not limited to", rather than an exclusive or exhaustive sense. In addition, the words "herein", "above", "below" and words of similar meaning, when used in this application, refer to this application as a whole and not to any particular portions of this application. Where the context permits, words in the Detailed Description using the singular or plural may also include the plural or singular, respectively. The word "or" in connection with a list of two or more items encompasses all of the following interpretations of that word, namely, any of the items in the list, all of the items in the list, and any combination of the items in the list. As used in this application, a reference to a layer "over" another layer means that the layers may be in direct contact or that there may be one or more intervening layers. As used in this application, a reference to a layer "on" another layer means that the layers are in direct contact. A reference to an element of the periodic table includes any isotope of that element.

[0032] The teachings of the technology provided herein may be applied to other systems, not necessarily the systems described below. Elements and acts of the various embodiments described below can be combined to provide further implementations of the technology. Some alternative implementations of the technology may include additional elements to those implementations described below, as well as fewer elements.

[0033] These and other changes may be made to the technology in light of the detailed description below. Although the description describes a particular embodiment of the technology and describes the best mechanism contemplated, no matter how detailed the description appears, the technology can be practiced in many ways. As described above, a particular term used when describing a particular feature or aspect of the technology should not be interpreted as implying that the term is redefined herein to be limited to any particular feature, characteristic, or aspect of the technology associated with the term. In general, the terms used in the following claims should not be interpreted as limiting the technology to the particular embodiments disclosed herein, unless the Detailed Description section otherwise explicitly defines such terms. Thus, the actual scope of the technology encompasses not only the disclosed embodiments, but also all equivalent ways of practicing or implementing the technology under the scope of the claims.

[0034] In order to reduce the number of claims, certain aspects of the technology are presented below in certain claim forms, but the applicant contemplates various aspects of the technology in any number of claim forms.

[0035] In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the implementation of the disclosed technology. However, it will be apparent to one skilled in the art that embodiments of the disclosed technology may be practiced without some of these specific details.

[0036] In some embodiments, the disclosure provides a compound of formula (I): [ka] X is Al or B.

[0037] R 1 is, independently in each occurrence, a substituent, and two R 1 The groups can be linked to form a ring.

[0038] M + is a cation.

[0039] In some preferred embodiments, R 1 None of the groups are linked. Optionally, according to these embodiments, each R 1 is independently 1-20 It is an alkyl group, one or more non-adjacent C atoms of the alkyl group may be replaced by O, S, CO, or COO, and one or more H atoms of the alkyl group may be replaced by F.

[0040] Preferred R 1 The group is C1- 20 alkyl, OR 1 One or more C atoms other than the C atom bonded to O or a terminal C atom may be replaced by O, and one or more H atoms may be replaced by F.

[0041] As used herein, the "terminal C atom" of an alkyl group means the C atom of a methyl group at the chain end of a straight-chain or branched alkyl group, respectively.

[0042] In some embodiments, each R 1 is the same.

[0043] In some embodiments, the compound has two or more different R 1 Contains a group.

[0044] In some embodiments, R of formula (I) 1The groups are linked so that the compound of formula (I) has the formula (Ia): [ka] In the formula, R 2 is, in each occurrence, independently a divalent organic group.

[0045] Optionally, R 2 is C 6-20 Optionally, the substituents are selected from arylene groups, such as 1,2-phenylene, which may be unsubstituted or substituted with one or more substituents, biarylene groups, such as 2,2′-linked biphenylene, ethylene, and propylene, each of which may be unsubstituted or substituted with one or more substituents. Optionally, the substituents are selected from F alkyl, C 1-12 One or more non-terminal C atoms of the alkyl may be replaced by F, 1-12 One or more C atoms of an alkyl may be replaced by O.

[0046] The compounds of formula (I) may be liquid at 25° C. and 1 atmosphere.

[0047] Preferably, M + is an alkali metal cation, more preferably a lithium cation.

[0048] Preferably, M + is a solvated cation.

[0049] Preferably, the solvent of the solvate is selected from solvents containing at least one ether group.

[0050] Preferably, the solvent contains two or more groups capable of coordinating to a metal cation.

[0051] The solvent may be selected from linear and cyclic compounds containing one or more ether groups, optionally with one or more groups selected from hydroxyl groups and carboxylate groups.

[0052] Exemplary solvents include, but are not limited to, tetrahydrofuran, dimethoxyethane, diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), and crown ethers, such as 12-crown-4 and 1-aza-12-crown-4.

[0053] The compounds may contain solvents of multiple solvation.

[0054] Optionally, the battery containing the compound of formula (I) does not contain any solvent or only a small amount of solvent, preferably M + The presence of small amounts of solvent has been found to greatly increase the ionic conductivity of compounds of formula (I). This increase is due to solvation of the cations, and when solvation occurs, the M + It will be understood that is solvated by at least some, but not necessarily all, of the solvent present. The presence of small amounts of organic solvents, such as ether-containing solvents, can increase ionic conductivity while greatly reducing flammability compared to ionic compounds dissolved in larger amounts of such solvents.

[0055] Thus, the formulation containing or consisting of a solvent and a compound of formula (I) preferably contains M + Preferably, the compound contains no more than 10 moles of solvent, more preferably no more than 7 moles or no more than 5 moles of solvent per mole of M + The formulation may contain only one solvate or may contain a mixture of two or more solvates.

[0056] The compound of formula (I) may be formed by reacting a compound of formula (II) with at least one compound selected from formulas (IIIa) and (IIIb). [ka]

[0057] Compounds of formula (IIIa) and (IIIb) can be prepared by reacting the desired R and R groups of formula (I) 2 It will be appreciated that the selection may be made according to the group.

[0058] Exemplary compounds of formula (I) include, but are not limited to, lithium aluminum hydride (LiAlH4), lithium borohydride (LiBH4).

[0059] Exemplary compounds of formula (IIIa) include: It may be non-fluorinated or may contain one or more, optionally all, C 1-20 The H atom of the alkyl may be replaced by F, 1-20 Alkyl monohydric alcohols, such as ethanol, isopropanol, 1H,1H,5H-octafluoro-1-pentanol, and pentadecafluoro-1-octanol; Ether monohydric alcohols, which may be non-fluorinated, partially fluorinated, or perfluorinated, such as 2-ethoxyethanol, diethylene glycol monoethyl ether, 1H,1H-perfluoro-3,6-dioxaheptan-1-ol, 1H,1H-perfluoro-3,6,9-trioxadecan-1-ol, 1H,1H-perfluoro-3,6-dioxadecan-1-ol, and 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol; and Monocarboxylic acid compounds, in which one or more non-adjacent C atoms other than the terminal C atom or the C atom adjacent to the carboxylic acid group may be replaced by O and one or more H atoms may be replaced by F, such as C 1-20 Examples include, but are not limited to, alkyl carboxylic acids. Examples include, but are not limited to, perfluoroalkyl carboxylic acids, such as trifluoroacetic acid, perfluoroalkyl ether carboxylic acids, and alkyl ether carboxylic acids.

[0060] Exemplary compounds of formula (IIIb) include R 2Included are alkanediols in which one or more non-adjacent non-terminal C atoms other than the C atom bonded to O of -O may be replaced with O; aromatic diols; dicarboxylic acids; and compounds having one hydroxyl and one carboxylic acid group, each of which may be unsubstituted or substituted with one or more substituents and may optionally be non-fluorinated, partially fluorinated, or perfluorinated.

[0061] Exemplary compounds of formula (IIIb) include ethylene glycol, catechol (1,2-dihydroxybenzene), oxalic acid, and their fluorinated derivatives.

[0062] In some embodiments, the reaction is carried out with only one compound selected from compounds of formula (IIIa) and (IIIb). According to these embodiments, R 1 Groups (hence, in the case of compounds of formula (II), each R 2 The radicals) are all the same.

[0063] In some embodiments, the reaction is carried out with two or more compounds selected from compounds of formula (IIIa) and (IIIb). According to these embodiments, the R groups can be different. Different R 1 The ratio of the groups may be selected according to the ratio of the compounds of formula (IIIa) and (IIIb) and their relative reactivities.

[0064] Metal cation M + When is a solvated cation, in some embodiments, a solvent for the solvate is present in the reaction mixture containing the compound of Formula (II) and the compounds of Formula (IIIa) and / or (IIIb).

[0065] In some embodiments, the solvent of a compound of formula (I) containing a solvated cation may be replaced with a different solvent. Methods of changing the solvent of a solvate include, but are not limited to, removing the solvent of the compound of formula (I) by heat treatment and replacing it with another solvent that can solvate the cation, and contacting the compound of formula (I) with a solvent that coordinates more strongly to the cation than the existing solvating solvent, for example, by treating a compound of formula (I) having a monodentate solvating solvent with a bidentate or tridentate or higher solvating solvent.

[0066] In some embodiments, the present disclosure provides a polymer comprising a repeat unit of formula (IV): [ka] where RG is a repeating group of the polymer and R 3 is a substituent, and X and M + However, as mentioned above.

[0067] R 3 is the above-mentioned polymer chain or substituent R 1 It could be.

[0068] The polymers may be formed by reacting a compound of formula (II) as described above with a starting polymer having backbone repeat groups substituted with hydroxyl or carboxylic acid groups. The reaction may be carried out in the presence of a compound of formula (IIIa) or (IIIb), and the ratio of polymeric to non-polymeric groups may be selected according to the ratio of starting polymer to compounds of formula (IIIa) and / or (IIIb) and their relative reactivities.

[0069] The polymer may be formed by reacting a compound of formula (I) above with a starting polymer.

[0070] The starting polymer can be, for example, cellulose, optionally in powder or fibrous form.

[0071] Purpose The single-ion conducting compound of formula (I) described herein may be provided in a rechargeable battery cell. The battery may be, but is not limited to, a metal battery or a metal ion battery, such as a lithium battery or a lithium ion battery.

[0072] The compound of formula (I) may be a component of a composite material that includes one or more additional materials, such as one or more polymers. A composition that includes a compound of formula (I) and a polymer may form a gel.

[0073] A layer comprising or consisting of a compound of formula (I) may be formed by depositing a formulation containing the material dissolved or dispersed in a solvent or solvent mixture. Optionally, a battery comprising a compound of formula (I) may be formed by depositing a formulation containing the material dissolved or dispersed in a solvent or solvent mixture. + and / or contains no more than 10 moles of solvent per mole of solvent and / or contains no solvent other than any solvating solvent.

[0074] The formulation may include a polymeric additional material dissolved in a solvent.

[0075] FIG. 1 shows a battery including an anode current collector 101 carrying an anode 103 on its surface, a cathode current collector 109 having a cathode 107 disposed on its surface, and a separator 105 disposed between the anode and cathode. The separator comprises or consists of a compound of formula (I). Preferably, the separator is a compound of formula (I) + and / or does not contain any solvent other than any solvating solvents described herein.

[0076] The battery may be a metal battery.The battery may be a metal ion battery.

[0077] In a metal battery, the negative electrode is a layer of metal (eg, lithium) that forms on the negative current collector during charging of the battery and peels off during discharging of the battery.

[0078] In the case of metal ion batteries, the negative electrode includes an active material for absorption of metal ions, such as graphite.

[0079] The positive electrode may be selected from any positive electrode known to one of skill in the art.

[0080] The negative and positive current collectors can be any suitable conductive material known to those skilled in the art, for example, one or more layers of a metal or metal alloy, such as aluminum or copper.

[0081] 1 shows a battery in which the negative and positive electrodes are separated only by a separator. In other embodiments, one or more additional layers may be disposed between the negative electrode and the separator and / or between the positive electrode and the separator.

[0082] FIG. 2 shows a battery, preferably a metal battery, including an anode current collector 101 carrying an anode 103 on its surface, a cathode current collector 109 having a cathode 107 disposed on its surface, a separator 105 disposed between the anode and the cathode, and an anode protection layer 111 disposed between the anode and the separator. The separator may include or consist of a compound described herein or any other separator known to those skilled in the art, such as a porous polymer in which a liquid electrolyte is absorbed. The anode protection layer includes or consists of a compound of formula (I) described herein. The anode protection layer may prevent or delay the formation of lithium metal dendrites in a metal battery. EXAMPLES

[0083] Compound Example 1-Synthesis 1 Compound Example 1 was prepared according to Scheme 1.

[0084] A solution of 2.15 mL of LiAlH4 in THF (1M) was added dropwise to a stirred solution of 1.19 mL of 2,2,3,3,4,4,5,5-octafluoropentan-1-ol (OFP) in dry THF (2 mL). The solution foamed during the addition. The rate of addition was controlled to prevent excessive foaming and heating. The mixture was then stirred at room temperature for 2 h.

[0085] The excess solvent was then removed under reduced pressure (3.0×10 -2The mixture was stirred at 37° C. for 30 mbar for 30 min. during this time to disperse any bubbles formed by the evaporating solvent. The mixture slowly concentrated to a thick oil and then to a viscous liquid and the stir bar was stopped. The sample was left under vacuum for an additional 5 min before the vacuum flask was sealed and transferred to a glove box. [ka]

[0086] The NMR spectrum of the product in deuterated THF is shown in Figure 3. The spectrum indicates that there are potentially two product species containing OFP units (6.2-6.8 and 4.2 ppm) and that approximately 10% of unreacted OFP is still present in the mixture (5.1 and 4 ppm).

[0087] From integration of the NMR peaks, we predicted that for every four molecules of OFP in the product mixture, there would be one molecule of THF present as residual solvent, and at least some of these were likely to form part of the solvate.

[0088] Compound Example 1-Synthesis 2 The reaction was carried out as described in Synthesis 1.

[0089] To a solution of OFP (5 mL, 35.8 mmol) in anhydrous 1,2-dimethoxyethane (1,2-DME) (10 mL) was added a solution of lithium aluminum hydride (9 mL, 9.0 mmol, 1.0 M in tetrahydrofuran) at 5° C. to room temperature. The resulting mixture was stirred at room temperature for 30 min and then heated to 60° C. for 30 min. Excess solvent was removed under reduced pressure (3.0×10 -2 mbar) at 25° C. for 4 h to give a thick gel.

[0090] in deuterated THF 1H NMR (600 MHz): δ (ppm), 3.29 (s, CH3 from 1,2-DME, 6.24H), 3.45 (s, CH2 from 1,2-DME, 4.22H), 4.16 (t, CF2CH2, J=14 Hz, 8H), 6.69 (tt, CF2CF2H, J=51.6 Hz, J=5.9 Hz, 4H).

[0091] From the integration of the NMR peaks (Figure 4), we predicted that for every four molecules of OFP in the product corresponding to one lithium cation, there would be 1.05 molecules of 1,2-DME present as residual solvent.

[0092] Preparation of electrolyte In an argon gas filled glove box, LiAl(OFP)4 obtained from synthesis 2 as a soft gel was weighed into a 20 mL bottle. Different amounts of 1,2-dimethoxyethane were then added to the gel (see Table 1) and the bottle was capped. The bottle was sonicated and placed on a roller for up to 1 hour to obtain a homogenous clear liquid. Electrolyte entry 5 in Table 1 was obtained by dissolving the remaining material adhering to the wall of the flask containing the parent LiAl(OFP)4 with 0.3 mL of 1,2-DME.

[0093] The electrolyte was dissolved in deuterated THF. 1 The product was analyzed by H NMR (FIGS. 5-9) and the 1,2-DME content was calculated from the integrals of the corresponding peaks (3.29 and 3.45 ppm) for four OFP molecules in the product corresponding to one lithium cation. [Table 1]

[0094] Compound Example 2 [ka] The reaction was carried out as described in Synthesis 1.

[0095] To a solution of OFP (5 mL, 35.8 mmol) in anhydrous 1,2-dimethoxyethane (10 mL) was added a solution of lithium borohydride (4.5 mL, 9.0 mmol, 2.0 M in tetrahydrofuran) at 5° C. to room temperature. The resulting mixture was stirred at room temperature for 30 min and then heated to 60° C. for 1 h. An in-process check NMR showed unreacted OFP. The solution was cooled to room temperature and lithium borohydride (0.8 mL, 1.6 mmol, 2.0 M in tetrahydrofuran) was added. The solution was heated to 60° C. for 1 h and cooled to room temperature. Excess solvent was removed under reduced pressure (3.2×10 -2 The mixture was heated to 80° C. at 37° C. for 2.5 h at 25° C. under reduced pressure to give a gel. OFP (0.8 mL, 5.8 mmol) was added, the mixture was heated to 80° C., 1,2-DME (1.5 mL) was added, the solution was stirred for 4.5 h, and the solution was then cooled to room temperature. Excess solvent was then removed under reduced pressure at 80° C. (3.8×10- 2 The mixture was transferred to an argon glove box at 37° C. (mbar, 3.5 h). NMR analysis showed some remaining OFP. The solid was redissolved in 10 mL of 1,2-DME at room temperature and 0.47 mL (0.94 mmol) of lithium borohydride (0.47 mL, 0.94 mmol, 2.0 M in tetrahydrofuran) was added dropwise at room temperature. The solution was heated to 60° C. for 1 h and lithium borohydride (0.06 mL, 0.12 mmol, 2.0 M in tetrahydrofuran) was added dropwise. The mixture was cooled to room temperature. Excess solvent was then removed under reduced pressure at 25° C. (37.8×10 -2 mbar for 30 min) to give a thick oil.

[0096] in deuterated THF 1 H NMR (600 MHz): δ (ppm), 3.28 (s, CH3 from 1,2-DME, 9.71 H), 3.44 (s, CH2 from 1,2-DME, 6.44 H), 3.96 (t, CF2CH2, J = 15.2 Hz, 8 H), 6.59 (tt, CF2CF2H, J = 51.2 Hz, J = 5.6 Hz, 4 H).

[0097] From the integration of the NMR peaks, we predicted that for every four molecules of OFP in the product corresponding to one lithium cation, there would be 1.62 molecules of 1,2-DME present as residual solvent.

[0098] Compound Example 3 [ka] The reaction was carried out as described in Synthesis 1.

[0099] To a solution of fluorinated diethylene glycol methyl ether (2.75 mL, 17.3 mmol) in anhydrous 1,2-dimethoxyethane (5 mL) was added a solution of lithium aluminum hydride (4.3 mL, 4.3 mmol, 1.0 M in tetrahydrofuran) at 15° C. to room temperature. The resulting mixture was stirred at room temperature for 30 min and then heated to 60° C. for 30 min. Excess solvent was removed under reduced pressure (3.7×10 -2 After evacuating at 1000 rpm for 2 h at 375° C., a thick gel was obtained. Additional 1,2-dimethoxyethane was added to the material to obtain a free-flowing liquid.

[0100] in deuterated THF 1 H NMR (600 MHz): δ (ppm), 3.28 (s, CH3 from 1,2-DME, 6.24H), 3.44 (s, CH2 from 1,2-DME, 4.22H), 4.05 (t, CF2CH2, J = 11.1 Hz, 8H)

[0101] From the integration of the NMR peaks, we predicted that for every four molecules of fluorinated diethylene glycol methyl ether in the product corresponding to one lithium cation, there would be 3.10 molecules of 1,2-DME present as residual solvent.

[0102] Electrochemical characterization Characterization of the ionic liquid formed in synthesis 1 was carried out on a two-electrode cell with Cu foil (Advent) as the working electrode and Li foil as the counter / reference electrode, respectively. The ionic liquid was manually deposited between the two electrodes connected to a potentiostat (CHI). Cyclic voltammetry measurements were performed to determine the current passing through the cell as a function of the applied potential difference at the electrodes. The experiment was carried out inside an Ar-filled glove box (MBRAUN). The potential of the Cu electrode was scanned between -2 V and +2 V vs. the Li electrode and the cyclic voltammetry plot is shown in Figure 10. Visual confirmation of Li metal deposition on the Cu foil was obtained using a digital photograph of the substrate (Figure 11) where the dark areas of the image are lithium metal.

[0103] Cell Example 1 - Compound of Synthesis 1 EIS measurements were carried out on a 2032-type coin cell device (casing purchased from Cambridge Energy Solutions) with a spacer of stainless steel disk (SS) made of four layers of Kapton tape (final thickness 260 microns) with a circular hole with a diameter of 0.6 cm in the center. The material containing compound Example 1, Synthesis 1 was spread to cover the hole. Two more stainless steel disks were placed on top of the stack. The symmetric cell was thoroughly dried and installed in an oxygen-free, Ar-filled MBraun glove box.

[0104] Cell Example 2 - Compound of Synthesis 2 The cell was fabricated by inserting a stainless steel spacer into the bottom of the coin cell described above, followed by a nylon mesh (Merck) with a thickness of 135 microns and a porosity of 47%. Thirty microliters of the electrolyte in Table 1 was drop cast onto the mesh. Two stainless steel spacers, a wave spring, and a coin cell top were positioned on the mesh, followed by crimping. The cell was assembled in an argon gas filled glove box (MBraun).

[0105] Cell Examples 3 to 6 Cell Examples 3-6 were formed as described for Cell Example 2, except that Electrolytes 2-5, respectively, from Table 1 were used in place of Electrolyte 1.

[0106] Cell Example 7 The cell was fabricated by inserting a stainless steel spacer into the bottom of the coin cell, followed by a fluorosilicone stencil. The stencil was molded as a 155 mm diameter disk with a 5 mm diameter circular hole in its center. 30 μL of compound Example 2 was filled into the hole. On top of the stencil, two stainless steel spacers were placed, followed by a wave spring and a coin cell top, then crimped. The thickness of the stencil in the crimped cell was 360 μm.

[0107] Electrochemical Impedance Spectroscopy (EIS) EIS measurements were performed at room temperature over a frequency range of 1 Hz to 1 MHz with an amplitude of 5 mV.

[0108] Calculate the conductivity using the following formula:

number

[0109] The Nyquist plot for Cell Example 1 is shown in FIG.

[0110] The Nyquist plots for Cell Examples 2 to 6 are shown in FIG.

[0111] The conductivities are shown in Table 2. [Table 2]

[0112] As shown in Table 2 and FIG. 14, increasing the solvate:cation ratio for a given material leads to an increase in conductivity.

Claims

1. A compound of formula (I) 【Chemistry 1】 In the formula, X is Al or B, and R １ is, independently in each occurrence, a substituent; １ The groups may be linked to form a ring, M ＋ is a cation.

2. The R １ The compound of claim 1 , wherein none of the groups are linked.

3. Each R １ But independently, C １－２０ The compound according to claim 2, wherein the alkyl group is an alkyl group, one or more non-adjacent C atoms of which may be replaced by O, S, CO, or COO, and one or more H atoms of which may be replaced by F.

4. Each R １ are independently selected from alkyl and alkyl ether groups, and one or more H atoms may be replaced with F.

5. Each R １ The compound according to any one of claims 2 to 4, wherein are the same.

6. The compound has at least two different R １ The compound according to any one of claims 1 to 4, which contains a group.

7. R in formula (I) １ groups are linked and the compound of formula (I) has the formula (Ia): 【Chemistry 2】 In the formula, R ２ The compound of claim 1 , wherein, in each occurrence, is independently a divalent organic group.

8. M ＋ The compound of claim 1 , wherein is an alkali metal ion.

9. M ＋ The compound of claim 8, wherein is a lithium ion.

10. M ＋ The compound of claim 1 , wherein is a solvated cation.

11. 11. The compound of claim 10, wherein the solvate of the solvent is selected from solvents containing at least one ether group.

12. The solvent: M ＋ A formulation comprising the compound of claim 11 and a solvent, wherein the molar ratio of is 10:1 or less.

13. The solvent: M ＋ 13. The formulation of claim 12, wherein the molar ratio of is at least 0.5:

1.

14. 13. A method of forming a compound of claim 1 comprising reacting a compound of formula (II) with at least one compound selected from formulas (IIIa) and (IIIb). 【Chemistry 3】

15. 15. The method of claim 14, wherein the compound of formula (IIIa) is selected from monohydric alcohols and monocarboxylic acids, and the compound of formula (IIIb) is selected from diols and dicarboxylic acids.

16. 15. The method of claim 14, wherein the reaction is carried out in a reaction mixture comprising the solvent of the solvate of claim 10.

17. 11. A method comprising at least partially replacing the solvent of the solvate of the compound of claim 10 with another solvent.

18. A polymer comprising a repeat unit of formula (IV): 【Chemistry 4】 where RG is a repeating group of the polymer, and R ３ is a substituent, X is Al or B, M ＋ is a cationic polymer.

19. 19. A metal or metal ion battery comprising a negative electrode, a positive electrode, and a compound according to claim 1 or a polymer according to claim 18 disposed between the negative electrode and the positive electrode.

20. The battery includes a solvent, and the solvent of the battery: M ＋ 20. The metal or metal-ion battery of claim 19, wherein the molar ratio of is 10:1 or less.

21. 20. The metal battery of claim 19, comprising an anode protection layer comprising the compound or polymer disposed between the anode and cathode.

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