Single-ion conducting networks

Abstract

A method of forming a single ion conducting network comprising reacting a first compound of formula (I) with a second compound and a third compound: Formula (I). X is selected from the group consisting of B and Al. + is a cation, e.g., a lithium ion. The second compound contains at least two hydroxyl groups, e.g., a diol. The third compound contains only one hydroxyl group. The single-ion conducting network can be used in metal or metal-ion batteries. JPEG2024517620000002.jpg647

Description

[Technical field]

[0001] Embodiments of the present disclosure relate to single-ion conductive materials, methods of making the single-ion conductive materials, and batteries containing the single-ion conductive materials.

[0002] Single ion conducting networks are known.

[0003] WO2020 / 072650 discloses an interfacial layer of a negative electrode comprising an ion-conducting network having anionic coordination units, organic linkers bonded through the anionic coordination units, and counterions dispersed within the ion-conducting organic network.

[0004] US 10,665,896 discloses single ion conducting polymer networks.

[0005] Zhenan Bao et al., “A Dynamic, Electrolyte-Blocking, and Single-Ion-Conductive Network for Stable Lithium-Metal Anodes,” Joule, Volume 3, Issue 11, 20 November 2019, Pages 2761-2776, discloses a single-ion conductive network formed by the reaction of lithium aluminum hydride, lithium borohydride, or silicon tetrachloride with 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol (FTEG).

[0006] WO2014 / 129972 is sp 3 Boron-based single-ion conducting polymers are disclosed. Summary of the Invention

[0007] In some embodiments, the present disclosure provides a method of forming a single-ion conducting network, comprising reacting a first compound of formula (I) with a second compound and a third compound, [XH4 ] - M + (I) During the ceremony, X is selected from the group consisting of B and Al; M + is a cation, The second compound comprises at least two hydroxyl groups; The third compound contains only one hydroxyl group.

[0008] Optionally, M + Li + It is.

[0009] Optionally, the second compound is a compound of formula (II): HO-L-OH (II) In the formula, L is a divalent organic group.

[0010] Optionally, the third compound is a compound of formula (III): HO-LR 3 (III) In the formula, L is a divalent organic group, R 3 is selected from F and H.

[0011] Optionally, L of formula (II) or formula (III) is a group of formula (IV): -[(A 1 ) p -Z] q -(A 2 ) r - (IV) During the ceremony, A at each appearance 1 and A 2 are independently unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, and CR 1 2 (Wherein, R 1 is H or a substituent; q is 0 or a positive integer, when q is a positive integer, p is at least 1; r is at least 1, Each occurrence of Z is independently O, S, or NR 4 , Si(R 5 ) 2 SO 2 , CO C=O, COO, or CONR 4 and R 4 is independently H or a substituent, and each occurrence of R 5 is a substituent.

[0012] Optionally, the hydroxyl groups of the second and third compounds are the only protic groups of these compounds.

[0013] Optionally, each R 1 is, independently, H; F; Linear, branched, or cyclic C 1-12 alkyl (wherein one or more non-adjacent, non-terminal C atoms may be replaced by O or COO and one or more H atoms may be replaced by F); anionic groups; and The photocrosslinkable group is selected from the group consisting of:

[0014] Optionally, each R 1 is independently H or F.

[0015] Optionally, the second compound is a dihydric alcohol.

[0016] Optionally, the second compound is a compound of formula (IIa): HO-(C 2 R 1 4 Z)n-(CR 1 2 ) r -OH (IIa) where R at each occurrence 1 is H or a substituent, n is at least 1, r is at least 1, and Z at each occurrence is independently O, S, NR 4 , Si(R 5 ) 2 SO 2 , CO C=O, COO, or CONR4 and R 4 is independently H or a substituent, and each occurrence of R 5 is a substituent.

[0017] Optionally, the third compound is a compound of formula (IIIa): HO-(C 2 R 1 4 Z) q -(CR 1 2 ) r -R 3 (IIIa) During the ceremony, R at each occurrence 1 is H or a substituent, q is at least 1; r is at least 1, Each occurrence of Z is independently O, S, or NR 4 , Si(R 5 ) 2 SO 2 , CO C=O, COO, or CONR 4 and R 4 is independently H or a substituent, and each occurrence of R 5 is a substituent.

[0018] Optionally, the molar ratio of the second compound to the third compound is from 99:1 to 1:99.

[0019] In some embodiments, the present disclosure provides single-ion conducting networks obtainable by the methods described herein.

[0020] In some embodiments, the present disclosure provides a single-ion conducting network comprising a group of formula (V): [XO 4 ] - M + (V) In the formula, X is selected from Al and B; M +is a cation, and the single ion conducting network comprises a group of formula (V) where at least one of the O atoms is bonded to an O atom of another group of formula (V) through an organic group L, and at least one of the O atoms is bonded to an organic group that is not bonded to another group of formula (V).

[0021] Optionally, the single-ion conductive network further comprises a group of formula (V), wherein each O atom of the group of formula (V) is bonded to an O atom of another group of formula (V) through an organic linking group L; Optionally, the organic group that is not bonded to another group of formula (V) is a group of formula (VI): -LR 3 (VI) where R at each occurrence 3 is independently H or F.

[0022] Optionally, the group L connected to the O atom of the group of formula (V) is a group of formula (IV), -[(A 1 ) p -Z] q -(A 2 ) r - (IV) During the ceremony, A at each appearance 1 and A 2 are independently unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, and CR 1 2 (Wherein, R 1 is H or a substituent; q is 0 or a positive integer, when q is a positive integer, p is at least 1; r is at least 1, Each occurrence of Z is independently O, S, or NR 4 , Si(R 5 ) 2 SO 2 , CO C=O, COO, or CONR 4 and R 4 is independently H or a substituent, and each occurrence of R 5 is a substituent.

[0023] In some embodiments, the present disclosure provides a metal or metal-ion battery comprising a negative electrode, a positive electrode, and a structure comprising a single-ion conducting network as described herein disposed between the negative electrode and the positive electrode.

[0024] Optionally, the structure comprises a single-ion conducting network and an additional material dispersed within the single-ion conducting network.

[0025] The additional material may be selected according to the desired mechanical properties of the composition comprising the single ion conducting network and the additional material.

[0026] Optionally, the additional material is an organic polymer, for example, cellulose.

[0027] Optionally, the anode protection layer disposed between the anode and the cathode comprises a single-ion conducting network.

[0028] In some embodiments, the present disclosure provides a method of forming a single-ion conducting network, comprising reacting a first compound of formula (VII) with a second compound and a third compound, Si(OR 6 ) u Y v (VII) In the formula, R 6 is the formula -An - M + (Wherein, An - is an anionic group, M + is an organic residue substituted with at least one group of Y is a leaving group, u is 1 or 2; v is 4-u, The second compound comprises at least two hydroxyl groups; The third compound contains two or more hydroxyl groups.

[0029] A "single-ion conducting network" as described herein comprises a network of anions connected to each other through linking groups and free cations. [Brief description of the drawings]

[0030] [Figure 1] 1 shows reactants for forming a single-ion conducting network according to some embodiments of the present disclosure. [Figure 2A] The products of the reaction of LiAlH4 with diols only are shown. [Figure 2B] 1 shows the products of reaction of LiAlH4 with monohydric alcohols and diols. [Diagram 3] FIG. 1 is a schematic diagram of a battery having a separator comprising a single-ion conducting network as described herein. [Figure 4] FIG. 1 is a schematic diagram of a battery having an anode protective layer comprising a single-ion conductive network as described herein.

[0031] 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

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] In some embodiments, the present disclosure provides a method of forming a single-ion conducting network, in which a first compound of formula (I) is reacted with a second compound and a third compound. [XH 4 ] - M + (I)

[0038] X is selected from the group consisting of Al and B.

[0039] M+ is a cation, preferably an alkali cation, more preferably Li + It is.

[0040] The second compound contains at least two hydroxyl groups.

[0041] The third compound has a single hydroxyl group.

[0042] FIG. 1 shows that the compound of formula (I) is LiAlH 4 1 shows a method according to some embodiments in which the second compound is a diol and the third compound is a monohydric alcohol. The black squares in FIG. 1 represent schematic groups other than hydroxyl at the chain end of the monohydric alcohol. This is because under the reaction conditions LiAlH 4 It is an inert group that does not react with

[0043] Upon reaction of the compound of formula (I) with a diol, an Al-O bond is formed and the hydroxyl group of the partially reacted diol leaves, which can then react with another Al atom to form a single ion conducting network as shown in FIG. 2A.

[0044] Upon reaction of the compound of formula (I) with a monohydric alcohol, an Al-O bond is still formed, but further reaction of the monohydric alcohol unit does not occur in the absence of the second hydroxyl group.

[0045] As a result, depending on the molar ratio of monohydric alcohol to diol, AlO 4 - Only one, two, or three of the four O atoms are connected to another AlO through a linker group L formed from a diol. 4 - is connected to

[0046] Therefore, the AlO 4 -The degree of interconnection between the centers can be controlled by selecting the number of reactive hydroxyl groups on the second compound and / or the molar ratio of the second compound to the third compound.

[0047] The degree of interconnection can be controlled to obtain single-ion conducting networks with desired properties. Properties that can be altered compared to fully interconnected networks include, but are not limited to, one or more of porosity, polymer dynamics, particularly polymer segment dynamics, and mechanical strength.

[0048] These properties can in turn affect the ionic conductivity of the single-ion conducting network.

[0049] Figures 1 and 2 show LiAlH 4 Although single-ion conducting networks formed from a monohydric alcohol, and a diol are shown, it will be understood that single-ion conducting networks may be formed from other first, second, and third materials described herein.

[0050] The crosslinked ion-conducting network may include groups of formula (V). [XO 4 ] - M + (V)

[0051] The network comprises a group of formula (V) in which each of the O atoms is bonded to another group of formula (V) through an organic linking group L, comprises a group of formula (V) in which at least one of the O atoms, and optionally one, two, or three of the O atoms, is not bonded to another group of formula (V) through an organic linking group L.

[0052] Preferably, the O atom not bonded to a group of formula (V) is bonded to a group of formula (VI), -LR 3 (VI) where R at each occurrence 3 is independently H or F.

[0053] X is selected from Al and B.

[0054] M + is a cation.

[0055] 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 linear alkyl group or the C atom of a methyl group at the chain end of a branched alkyl group, respectively.

[0056] The aluminum-oxygen bonds of the dynamic single-ion conductive networks described herein may break under mechanical stress, for example due to volume changes resulting from the insertion and release of metal cations from the electrodes of rechargeable batteries containing the networks. These bonds may be able to reform, which may allow cracks or pinholes in the dynamic single-ion conductive networks to close spontaneously (self-heal), thereby inhibiting the formation of metal dendrites.

[0057] First Compound Exemplary compounds of formula (I) include lithium aluminum hydride (LiAlH 4 ), lithium borohydride (LiBH 4 ), and lithium tetrahydrogallate (LiGaH 4 ), but are not limited to:

[0058] The single-ion conducting network may contain only one of the Al and B anions. The single-ion conducting network may contain both the Al and B anions.

[0059] The second and third compounds The second compound contains at least two hydroxyl groups. Preferably, the second compound contains only two hydroxyl groups.

[0060] The third compound contains only hydroxyl groups.

[0061] Optionally, the second compound is a compound of formula (II). HO-L-OH (II)

[0062] L is a divalent organic group.

[0063] Preferably, L is selected from the group of formula (IV). -[(A 1 ) p -Z] q -(A 2 ) r - (IV)

[0064] A at each appearance 1 and A 2 are independently unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, and CR 1 2 (Wherein, R 1 is H or a substituent.

[0065] q is 0 or a positive integer.

[0066] If q is a positive integer, then p is at least one.

[0067] In a preferred embodiment, q is at least 1, more preferably 1 to 6, and each A 1 CR 1 2 According to these embodiments, p is preferably 2.

[0068] r is at least 1, preferably 1 or 2.

[0069] Z is O, S, NR 4 , Si(R 5 ) 2 SO 2 , CO C=O, COO, or CONR 4 and R 4 is independently H or a substituent, and each occurrence of R 5 is a substituent.

[0070] In a preferred embodiment, r is 1 and A 2 is an arylene or heteroarylene group.

[0071] In another preferred embodiment, each A 2 CR 1 2 According to these embodiments, r is preferably 2.

[0072] Preferably, each occurrence of R 1 teeth, H, F, and Linear, branched or cyclic alkyl, optionally C 1-20 Alkyl (wherein one or more non-adjacent, non-terminal C atoms are O, S, NR 4 , Si(R 5 ) 2 SO 2 , CO, COO, or CONR 4 and one or more H atoms may be replaced by F, and each occurrence of R 4 is independently H or a substituent, and each occurrence of R 5 is a substituent), anionic substituents, and The photocrosslinkable group is selected from the group consisting of:

[0073] Anionic Substituent R 1 The presence of may increase one or more of the ionic conductivity of the network, the solubility of the network in polar organic solvents or water, and adhesion, as compared to a network in which the aluminum acid or borate groups formed after reaction of the compound of formula (I) are the only anionic groups in the network.

[0074] Exemplary anionic substituents are C substituted with one or more anionic groups. 1-12 Alkyl, aryl (e.g., phenyl), or C 1-12 Alkylene aryl, C 1-12 One or more non-adjacent, non-terminal C atoms of an alkyl or alkylene may be O, S, NR 4 , Si(R 5 )2 , S.O. 2 , CO, COO, or CONR 4 The anionic substituent can be a sulfonic acid (-SO 3 -) The charge of the anion is preferably the cation M of formula (I) + , more preferably Li + is the same as the cation M + It will be appreciated that a balance is maintained.

[0075] The photocrosslinkable groups may be crosslinked after reaction of the first, second, and third compounds to increase the degree of crosslinking within the single-ion conducting network. An exemplary photocrosslinkable group is an azide-containing group.

[0076] Preferably, each R 1 is independently H or F.

[0077] Preferred arylene or heteroarylene groups A 1 Or A 2 is phenylene.

[0078] An arylene or heteroarylene group A 1 Or A 2 Even if unsubstituted, F, CN, NO 2 , and linear, branched, or cyclic C 1-12 alkyl, one or more non-adjacent, non-terminal C atoms may be replaced by O or COO, and one or more H atoms may be replaced by F.

[0079] Optionally, R for each occurrence 4 is H or linear, branched, or cyclic C 1-12 alkyl, one or more non-adjacent C atoms other than the C atom bonded to N, or terminal C atoms may be replaced by O, S, CO, or COO, and one or more H atoms may be replaced by F or anionic groups, such as SO 3- may be replaced by

[0080] Each R 4 is preferably H or a linear, branched or cyclic C 1-12 one or more non-adjacent or terminal C atoms other than the C atom bonded to N selected from alkyl may be replaced by O; one or more H atoms may be replaced by F.

[0081] Optionally, R for each occurrence 5 is H or linear, branched, or cyclic C 1-12 alkyl, one or more non-adjacent C atoms other than the C atom bonded to Si, or terminal C atoms may be replaced by O, S, CO, or COO, and one or more H atoms may be replaced by F or anionic groups, such as SO 3 - may be replaced by

[0082] Each R 5 is preferably H or a linear, branched or cyclic C 1-12 one or more non-adjacent or terminal C atoms other than the C atom bonded to Si selected from alkyl may be replaced by O, and one or more H atoms may be replaced by F.

[0083] An exemplary second compound is a diol, more preferably a compound of formula (IIa): HO-(C 2 R 1 4 Z)n-(CR 1 2 ) r -OH (IIa) During the ceremony, Z is O, S, NR 4 , Si(R 5 ) 2 SO 2 , CO C=O, COO, or CONR 4 and R 4 and R 5is as described above, n is at least 1 and optionally 1 to 6, r is at least 1 and preferably 1 or 2, and each R 1 , Z, R 4 , and R 5 is as defined above.

[0084] Each R 1 is preferably H or F. Each Z is preferably O.

[0085] Exemplary compounds of formula (IIa) include: HO-CH 2 CF 2 -(OC 2 F 4 ) 2 -CF 2 CH 2 -OH

[0086] Optionally, the third compound is a compound of formula (III): HO-LR 3 (III) In the formula, L is as defined above, and R 3 is selected from F and H.

[0087] An exemplary third compound is a compound of formula (IIIa): HO-(C 2 R 1 4 Z) q -(CR 1 2 ) r -R 3 (IIIa) In the formula, q, r, Z, and R 1 is as described above, and R 3 is H or F.

[0088] Exemplary compounds of formula (IIIa) include: HO-CH 2 CF 2 -(OC 2 F 4 ) 2 -CF2 CF 2 CF 3 HO-CH 2 CF 2 -(OC 2 F 4 ) 2 -CF 2 CF 3 HO-CH 2 CF 2 -(OC 2 F 4 ) 2 -CF 3

[0089] Optionally, the molar ratio of the second compound to the third compound is in the range of 99:1 to 1:99.

[0090] In some embodiments, only one second compound is used. In some embodiments, two or more different second compounds are used.

[0091] In some embodiments, only one third compound is used. In some embodiments, two or more different third compounds are used.

[0092] Silicate-containing single-ion conducting networks The single ion conducting network containing silicic acid may be formed by reacting a first compound of formula (VII) with a second compound and a third compound, Si(OR 6 ) u Y v (VII) In the formula, R 6 is the formula -An - M + (Wherein, An - is an anionic group, M + is an organic residue substituted with at least one group of Y is a leaving group, preferably a halide, more preferably Br, Cl, or I, most preferably Cl; u is 1 or 2; v is 4-u, The second compound comprises at least two hydroxyl groups; The third compound contains only one hydroxyl group.

[0093] The second and third compounds may be as described anywhere herein.

[0094] The single-ion conducting network formed by this method has the formula SiO u Y v The O atom of this group can be linked by an organic linker L to the group of formula SiO u Y v and the O atom of this group is linked to another group of the formula SiO u Y v It will be understood that the group is not linked to any other group.

[0095] R 6 is substituted with one or more groups An - M + is preferably represented by the formula -L-(An - M + ) w where L is as defined above and w is at least 1, preferably 1. - is preferably -SO 3 - It is.

[0096] Additive Compounds In some embodiments, the single-ion conducting network may be formed exclusively from the first, second, and third compounds.

[0097] In some embodiments, the single-ion conductive network may include one or more additional groups formed from the reaction of one or more additive compounds.

[0098] The additive compound may be selected from non-ionic compounds capable of reacting with the second and third compounds. The additive compound may be a silane, e.g., C 1-12 Alkyl group, C 1-12The additive compound may be a silane substituted with a group selected from an alkoxy group and a halide group, the silane being substituted with at least one halide group. An exemplary additive compound is tetrachlorosilane.

[0099] The identity and proportion of the additive compounds can be selected to adjust one or more properties of the single-ion conductive network, such as the degree of crosslinking and surface properties (eg, hydrophilicity) of the network.

[0100] Purpose The single-ion conductive materials described herein may be provided in a battery, which 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.

[0101] The single-ion conductive material may be a component of a composite material that includes one or more additional materials. A layer that includes or consists of a single-ion conductive material may be formed by depositing a formulation containing the material dissolved or dispersed in a solvent or solvent mixture, followed by evaporation of the solvent.

[0102] 3 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 includes or consists of a single-ion conducting network as described herein.

[0103] 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.

[0104] In the case of metal ion batteries, the negative electrode includes an active material for absorption of metal ions, such as graphite.

[0105] The positive electrode may be selected from any positive electrode known to one of skill in the art.

[0106] 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.

[0107] 3 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.

[0108] FIG. 4 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 protective layer 111 disposed between the anode and the separator. The separator may include or consist of a single-ion conductive network as described herein, or any other separator known to those skilled in the art, such as a porous polymer with a liquid electrolyte absorbed therein. The anode protective layer may include or consist of a single-ion conductive network as described herein. The anode protective layer may prevent or delay the formation of lithium metal dendrites in a metal battery.

[0109] In some embodiments, the single-ion conducting network can be used in a battery without any liquid electrolyte absorbed therein.

[0110] In some embodiments, the electrolyte is absorbed within the single-ion conducting network described herein.

[0111] The electrolyte can be an organic solvent or a blend of organic solvents. The solvent is optionally an alkyl carbonate or a mixture of organic carbonates, such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate, vinylene carbonate, dimethoxyethane, diglyme, triglyme, tetraglyme, tetrahydrofuran, dioxolane, acetonitrile, adiponitrile, dimethylsulfoxide, dimethylformamide, nitromethane, N-methylpyrrolidone, ionic liquids, deep eutectic solvents, and mixtures thereof.

[0112] Salts with metal cations, such as lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) or lithium hexafluorophosphate Li bis(fluorosulfonyl)imide (LiFSI), LiAsF 6 , LiSbF 6 , LiClO 4 , Li bis(oxalato)boric acid, LiBF 4 , LiNO 3 , Li halides, Li dicyanamide, and combinations thereof may be dissolved in the electrolyte solvent. EXAMPLES

[0113] 410 mg of 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol (FTEG) was added to a container containing less than 0.1 ppm O 2 and H 2 In a nitrogen glove box with O, the compounds were dissolved in 3 ml of THF along with 1, 5, or 10 wt % fluorinated diethylene glycol monomethyl ether.

[0114] LiAlH in THF under nitrogen and continuous stirring. 4 500, 520, and 540 microliters of a 1 M solution of was added dropwise to solutions having 1, 5, and 10 wt. % fluorinated diethylene glycol monomethyl ether, respectively. The mixtures were left overnight.

[0115] The solution was then spread onto a copper foil in a nitrogen-filled glove box to obtain a layer with a thickness in the range of 100-200 nm.

Claims

1. 1. A method for forming a single-ion conducting network comprising reacting a first compound of formula (I) with a second compound and a third compound, [XH ４ ] － M ＋ (I) wherein X is selected from the group consisting of B and Al; M ＋ is a cation, the second compound comprises at least two hydroxyl groups; The method, wherein said third compound contains only one hydroxyl group.

2. M ＋ But Li ＋ The method of claim 1, wherein

3. the second compound is a compound of formula (II), HO-L-OH (II) 2. The method of claim 1 , wherein L is a divalent organic group.

4. the third compound is a compound of formula (III), HO-L-R ３ (III) In the formula, L is a divalent organic group, R ３ The method of claim 1 , wherein is selected from F and H.

5. L is a group of formula (IV), -[(A １ ) ｐ -Z] ｑ -(A ２ ) ｒ - ('V) During the ceremony, A at each appearance １ and A ２ are independently unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, and CR １ ２ (Wherein, R １ is H or a substituent; q is 0 or a positive integer; when q is a positive integer, p is at least 1; r is at least 1; Z at each occurrence is independently O, S, or NR ４ , Si(R ５ ) ２ SO ２ , CO C═O, COO, or CONR ４ and R ４ is independently H or a substituent, and each occurrence of R ５ The method of claim 3 , wherein is a substituent.

6. Each R １ But independently, H; F; Linear, branched, or cyclic C １－１２ alkyl (wherein one or more non-adjacent, non-terminal C atoms can be replaced by O or COO and one or more H atoms can be replaced by F); anionic groups; and The method of claim 5 , wherein the photocrosslinkable group is selected from the group consisting of:

7. Each R １ The method of claim 6 , wherein is independently H or F.

8. The method of claim 1 , wherein the second compound is a dihydric alcohol.

9. the second compound is a compound of formula (IIa), 89-(3) ２ 2 １ ４ Z)n-(3R １ ２ )r-O2 (9ｩa) where R at each occurrence １ is H or a substituent, n is at least 1, r is at least 1, and Z at each occurrence is independently O, S, NR ４ , Si(R ５ ) ２ SO ２ , CO C═O, COO, or CONR ４ and R ４ is independently H or a substituent, and each occurrence of R ５ The method of claim 3 , wherein is a substituent.

10. the third compound is a compound of formula (IIIa), HO-(C ２ R １ ４ Z) ｑ -(CR １ ２ )r-R ３ (IIa) During the ceremony, R at each appearance １ is H or a substituent; q is at least 1; r is at least 1; Z at each occurrence is independently O, S, or NR ４ , Si(R ５ ) ２ SO ２ , CO C═O, COO, or CONR ４ and R ４ is independently H or a substituent, and each occurrence of R ５ The method of claim 4 , wherein is a substituent.

11. 2. The method of claim 1, wherein the molar ratio of the second compound to the third compound is from 99:1 to 1:

99.

12. A single-ion conducting network obtainable by the method according to any one of claims 1 to 11.

13. A single ion conducting network comprising a group of formula (V): [XO ４ ] － M ＋ (V) wherein X is selected from Al and B; ＋ is a cation, the single-ion conducting network comprising a group of formula (V), at least one of the O atoms being bonded to an O atom of another group of formula (V) through an organic group L, and at least one of the O atoms being bonded to an organic group that is not bonded to another group of formula (V).

14. 14. The single-ion conducting network of claim 13 further comprising a group of formula (V), wherein each of said O atoms of the group of formula (V) is bonded to an O atom of another group of formula (V) through an organic linking group L.

15. the organic group that is not bonded to another group of formula (V) is a group of formula (VI), -L-R ３ (VI) where R at each occurrence ３ is independently H or F.

16. L is a group of formula (IV), -[(A １ ) ｐ -Z] ｑ -(A ２ ) ｒ - ('V) During the ceremony, A at each appearance １ and A ２ are independently unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, and CR １ ２ (Wherein, R １ is H or a substituent; q is 0 or a positive integer; when q is a positive integer, p is at least 1; r is at least 1; Z at each occurrence is independently O, S, or NR ４ , Si(R ５ ) ２ SO ２ , CO C═O, COO, or CONR ４ and R ４ is independently H or a substituent, and each occurrence of R ５ The single-ion conducting network of claim 13 , wherein: is a substituent.

17. 13. A metal or metal ion battery comprising a negative electrode, a positive electrode, and a structure comprising the single-ion conductive network of claim 12 disposed between the negative electrode and the positive electrode.

18. 20. The metal or metal-ion battery of claim 17, wherein the structure comprises the single-ion conducting network and an additional material.

19. 20. The metal or metal-ion battery of claim 18, wherein the additional material is an organic polymer dispersed within the single-ion conducting network.

20. 18. The metal battery of claim 17, wherein the structure is an anode protective layer disposed between the anode and the cathode.

21. 1. A method for forming a single-ion conducting network comprising reacting a first compound of formula (VII) with a second compound and a third compound, Si(OR ６ ) ｕ Y ｖ (VII) In the formula, R ６ is represented by the formula -An － M ＋ (Wherein, An － is an anionic group, M ＋ is a cation; Y is a leaving group; u is 1 or 2; v is 4-u; the second compound comprises at least two hydroxyl groups; The method, wherein said third compound contains only one hydroxyl group.

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