Polymer, electrolyte composition, battery, and compound

Abstract

One aspect of the present disclosure provides a polymer containing a structural unit A represented by general formula (A) and a structural unit B represented by general formula (B), wherein the proportion of the structural unit A contained in the polymer is 20%-80%, and the proportion of the structural unit B is 20%-80%. [In general formula (A), R1 to R4 are each independently a hydrogen atom, a halogen atom, a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent aryl group having 1 to 20 carbon atoms; X1 is an oxygen atom, a divalent alkanediyl group having 1 to 20 carbon atoms, or a divalent arylene group having 1 to 20 carbon atoms; and -CH2- groups constituting the alkanediyl group may be partially substituted with -O- or the like.] [In general formula (B), R5 to R7 are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; X2 is a divalent functional group having 1 to 20 carbon atoms; at least one of carbon atoms of the functional group is a sp3 hybridized carbon atom; Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z- is an anionic functional group; and M is a lithium atom, a sodium atom, or a potassium atom.]

Description

Polymer, electrolyte composition, battery, and compound

[0001] The present disclosure relates to polymers, electrolyte compositions, and batteries, and compounds.

[0002] Batteries that use metal ions as charge carriers for charging and discharging (e.g., lithium ion batteries) have been the subject of vigorous research due to their high capacity. Known electrolytes used in such batteries include solutions of alkali metal salts containing organic solvents or ionic liquids. Meanwhile, research into solid electrolytes and polymer electrolytes has been ongoing as alternatives to liquid electrolytes, with a view to improving safety and processability (see Patent Documents 1 and 2).

[0003] Although lithium-ion batteries are superior in terms of battery performance, reserves of the raw material lithium are said to be smaller than those of other alkali metals, and research is also underway to improve the performance of batteries that use alkali metal ions other than lithium (e.g., sodium, potassium, etc.) as charge carriers.

[0004] Korean Patent Publication No. 10-2016-0050870 Special Publication No. 2023-511906

[0005] As lithium-ion batteries become more widespread, it is desirable for batteries that use metal ions as charge carriers for charging and discharging to have a wider range of electrolyte options to suit the environment in which they are used.

[0006] An object of the present disclosure is to provide a novel polymer that can be used as a polymer electrolyte. Another object of the present disclosure is to provide an electrolyte composition and a battery containing the polymer. Another object of the present disclosure is to provide a novel compound having an alkali metal-substituted carbonylsulfonylimide group.

[0007] The present disclosure provides the following [1] to

[11] .

[0008] [1] A polymer comprising a structural unit A represented by the following general formula (A) and a structural unit B represented by the following general formula (B), wherein, based on all structural units contained in the polymer, the proportion of the structural unit A is 20 to 80%, and the proportion of the structural unit B is 20 to 80%. [In general formula (A), R １ ~R ４ are each independently a hydrogen atom, a halogen atom, a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent aryl group having 1 to 20 carbon atoms; １ represents an oxygen atom, a divalent alkanediyl group having 1 to 20 carbon atoms, or a divalent arylene group having 1 to 20 carbon atoms, and —CH ２ A part of the - group may be substituted with -O-, -NH-, -(C═O)-, -(C═O)-O-, -O-(C═O)-, -(C═O)-NH-, or -NH-(C═O)-.] [In general formula (B), R ５ ~R ７ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom.] [2] The polymer according to [1], wherein in the structural unit B, M is a lithium atom or a sodium atom. [3] The -Z in the structural unit B － M ＋ [4] The polymer according to any one of [1] to [3], wherein the partial structure represented by the following formula (B-1) is a functional group selected from the group consisting of a lithiated sulfonic acid group, a lithiated carboxy group, a lithiated sulfonylimide group, and a lithiated carbonylsulfonylimide group. [4] The polymer according to any one of [1] to [3], wherein the structural unit B contains at least one of a structural unit represented by the following formula (B-1) and a structural unit represented by the following formula (B-2): [In general formula (B-1), R５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom. [In general formula (B-2), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom.] [5] The polymer according to any one of [1] to [4], which is composed of the structural unit A and the structural unit B, and is an alternating copolymer or a random copolymer. [6] An electrolyte composition comprising the polymer according to any one of [1] to [5]. [7] The electrolyte composition according to [6], which further comprises an organic solvent. [8] The electrolyte composition according to [6], which further comprises an alkali metal salt. [9] The electrolyte composition according to [6], which further comprises an organic solvent and an alkali metal salt.

[10] A battery comprising the polymer according to any one of [1] to [5] or the electrolyte composition according to any one of [6] to [9].

[11] A compound represented by the following general formula (b-1) or the following general formula (b-2): [In general formula (b-1), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom. [In general formula (b-2), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom.

[0009] According to the present disclosure, a novel polymer usable as a polymer electrolyte can be provided. According to the present disclosure, an electrolyte composition and a battery containing the polymer can also be provided. According to the present disclosure, a novel compound having an alkali metal-substituted carbonylsulfonylimide group can also be provided.

[0010] Fig. 1 is a graph showing the evaluation results of DC current density for an evaluation cell using the electrolyte composition of Example 1. Fig. 2 is a graph showing the evaluation results of DC current density for an evaluation cell using the electrolyte composition of Reference Example 1.

[0011] Hereinafter, embodiments of the present disclosure will be described, occasionally with reference to the drawings. However, the following embodiments are merely examples for explaining the present disclosure, and are not intended to limit the present disclosure to the following content. In this specification, a numerical range indicated with the symbol "to" includes a lower limit and an upper limit. In other words, a numerical range indicated as "x to y" means a range equal to or greater than x and equal to or less than y.

[0012] Unless otherwise specified, the materials exemplified in this specification can be used singly or in combination of two or more. When a plurality of substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.

[0013] One embodiment of the polymer is a polymer containing a structural unit A represented by the following general formula (A) and a structural unit B represented by the following general formula (B). In the polymer, the proportion of the structural unit A is 20 to 80% and the proportion of the structural unit B is 20 to 80% based on all structural units contained in the polymer. In the general formulas (A) and (B), * represents a bonding portion between each structural unit and another structural unit. The polymer contains an alkali metal ion (M ＋ ) and can be used as a polymer electrolyte.

[0014]

[0015] In general formula (A), R １ ~R ４ each independently represents a hydrogen atom, a halogen atom, a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent aryl group having 1 to 20 carbon atoms. １ represents an oxygen atom, a divalent alkanediyl group having 1 to 20 carbon atoms, or a divalent arylene group having 1 to 20 carbon atoms. ２ A part of the - group may be substituted by -O-, -NH-, -(C=O)-, -(C=O)-O-, -O-(C=O)-, -(C=O)-NH-, or -NH-(C=O)-.

[0016]

[0017] In general formula (B), R ５ ~R ７ X each independently represents a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms. ２ represents a divalent functional group having 1 to 20 carbon atoms. At least one of the carbon atoms of the functional group is sp ３ Y represents a nitrogen atom, an oxygen atom, and a sulfur atom. Z － represents an anionic functional group, and M represents a lithium atom, a sodium atom, or a potassium atom.

[0018] The conventional polymers having an anionic functional group alkali-metallated with an alkali metal (M) introduced into the side chain are -X in the above general formula (B). ２This is based on the technical idea that immobilizing anionic functional groups on the polymer backbone without using divalent functional groups such as α- and β-alkanoates facilitates the selective transport of alkali metal ions. In this molecular design, the anionic functional groups having counterions to alkali metal ions are immobilized on the polymer backbone, which immobilizes the chemical environment surrounding the alkali metal ions, potentially limiting the mobility of the alkali metal ions. Therefore, there is room for improvement when considering applications requiring higher ionic conductivity. While it is conceivable to reduce the incorporation rate of alkali metal-modified anionic functional groups into the polymer to weaken the binding of alkali metal ions by neighboring anionic functional groups, this may not be beneficial because it reduces the incorporation rate of alkali metal ions themselves.

[0019] In contrast, the polymer according to the present disclosure has an anionic functional group (-Z) alkali-metallated with at least one alkali metal (M) selected from the group consisting of lithium, sodium, and potassium. － In the structural unit B, the anionic functional group is in the form of an sp ３ A divalent functional group (-X) having at least one hybridized carbon atom ２ Since the connection is via a divalent functional group (a group represented by -), the mobility of the divalent functional group allows the anionic functional group to move relatively freely compared to when the divalent functional group is not used. By introducing the above-described structure, the distance between the anionic functional groups becomes non-uniform, making it possible to create a partial environment in which the alkali metal ions are loosely bound, and it is believed that the movement of the alkali metal ions in the polymer becomes easier, thereby improving the ionic conductivity of the alkali metal ions. It is presumed that the activation energy for the conduction of alkali metal ions can be reduced by providing a partial environment in which the alkali metal ions are loosely bound as described above.

[0020] Furthermore, for example, in the case of a polymer consisting only of the structural unit B, the anionic functional groups are located closer to each other than in the case of containing the structural unit A. As a result, the effect of connecting the anionic functional groups via the divalent functional group cannot be fully utilized. Therefore, in the polymer according to this embodiment, by containing both the structural unit A and the structural unit B, it is difficult to form a continuous structure of the structural unit B, and strong ionic interactions between the anionic functional groups and the alkali metal ions are suppressed, thereby improving the mobility of the alkali metal ions in the polymer and enabling further increase in ionic conductivity.

[0021] In the structural unit A, R １ ~R ４ are each independently a hydrogen atom, a halogen atom, a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent aryl group having 1 to 20 carbon atoms, and R １ ~R ４ is preferably a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms. １ ~R ４ At least two of R are preferably hydrogen atoms. １ ~R ４ It is preferable that at least three of R are hydrogen atoms. １ ~R ４ It is more preferable that all of are hydrogen atoms.

[0022] In the structural unit A, R １ ~R ４ are each independently a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent aryl group having 1 to 20 carbon atoms. The number of carbon atoms in the alkyl group may be, for example, 1 to 15, 1 to 10, 1 to 6, 1 to 5, 1 to 3, or 1. When the alkyl group has 3 or more carbon atoms, it may be a linear, branched, or cyclic hydrocarbon group, and is preferably a linear hydrocarbon group. The number of carbon atoms in the aryl group may be, for example, 4 to 20, 5 to 15, 6 to 8, or 6.

[0023] In the structural unit A, X １represents an oxygen atom, a divalent alkanediyl group having 1 to 20 carbon atoms, or a divalent arylene group having 1 to 20 carbon atoms. １ When X is an alkanediyl group, the number of carbon atoms in the alkanediyl group may be, for example, 2 to 20, 3 to 20, 3 to 15, 3 to 10, 3 to 8, or 3 to 6. When the number of carbon atoms in the alkanediyl group is 3 or more, the alkanediyl group may be a linear, branched, or cyclic hydrocarbon group, or may be a cyclic hydrocarbon group. １ When X is an arylene group, the number of carbon atoms in the arylene group may be, for example, 4 to 20, 5 to 15, 6 to 8, or 6. １ is preferably an arylene group, more preferably a benzenediyl group.

[0024] In the structural unit A, X １ is an arylene group having 6 carbon atoms, and R １ ~R ４ When all of the structural units are hydrogen atoms, the structural unit A can also be said to be a monomer unit when styrene is used as a monomer.

[0025] The structural unit B is —(C═O)—Y—X relative to the main chain carbon. ２ -Z connected via - － M ＋ The partial structure is a functional group having lithium ions, sodium ions, and potassium ions, and the polymer can conduct these alkali metal ions. － is an anionic functional group. In the structural unit B, M is a lithium atom, a sodium atom, or a potassium atom, but may be a lithium atom, a sodium atom, or a lithium atom.

[0026] -Z in structural unit B － M ＋The partial structure represented by the formula (I) may be an alkali metal-substituted functional group. In this specification, the alkali metal-substituted functional group refers to a group in which an anionic functional group, which is a conjugate base of the acid form of the functional group, forms a salt with an alkali metal ion. Specific examples of the alkali metal-substituted functional group include an alkali metal-substituted phenolic hydroxyl group, an alkali metal-substituted carboxylic acid group, an alkali metal-substituted sulfonic acid group, an alkali metal-substituted sulfonylimide group, and an alkali metal-substituted carbonylsulfonylimide group. The alkali metal-substituted phenolic hydroxyl group, an alkali metal-substituted carboxylic acid group, an alkali metal-substituted sulfonic acid group, and an alkali metal-substituted sulfonylimide group may be used.

[0027] The alkali metal phenolic hydroxyl group is an —OM group (—O M group) in which H of the —OH group, which is a phenolic hydroxyl group, is substituted with an alkali metal element M. － M ＋ An alkali metal carboxylic acid group refers to a —COOM group ([—COO] group) in which H of a carboxylic acid group (—COOH group) is substituted with an alkali metal element M, for example. － M ＋ The alkali metal sulfonic acid group refers to a sulfonic acid group (-SO ３ H group) in which H is substituted with an alkali metal element M ３ M group ([-SO ３ ] － M ＋ group), and examples thereof include a lithiated sulfonic acid group.

[0028] The alkali metal sulfonylimide group is a sulfonylimide acid group (-SO ２ -NH-SO ２ -SO in which H of the -R group is substituted with an alkali metal element M ２ -NM-SO ２ -R group ([-SO ２ -N-SO ２ -R] － M ＋ The alkali metal carbonylsulfonylimido group refers to a carbonylsulfonylimido group (-SO２ -NH-(C=O)-R group) in which H is substituted with an alkali metal element M ２ -NM-(C=O)-R group ([-SO ２ -N-(C=O)-R] － M ＋ group), and examples thereof include a lithium carbonylsulfonylimide group. The terminal R in the alkali metal sulfonylimide group and alkali metal carbonylsulfonylimide group may be a linear, branched, or cyclic hydrocarbon group. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and at least a portion of the hydrogen atoms constituting the hydrocarbon group may be substituted with halogen atoms, and the hydrocarbon group may be a halogenated hydrocarbon. Specific examples of the terminal R in the alkali metal sulfonylimide group and alkali metal carbonylsulfonylimide group include -CF ３ , and -C ６ H ５ etc. are also acceptable.

[0029] -Z in structural unit B － M ＋ The partial structure represented by the formula (I) may be, for example, a functional group selected from the group consisting of a lithiated phenol group, a lithiated sulfonic acid group, a lithiated carboxy group, a lithiated sulfonylimide group, and a lithiated carbonylsulfonylimide group; it may be a functional group selected from the group consisting of a lithiated phenol group, a lithiated sulfonic acid group, a lithiated carboxy group, and a lithiated sulfonylimide group; or it may be a functional group selected from the group consisting of a lithiated sulfonic acid group, a lithiated carboxy group, and a lithiated sulfonylimide group.

[0030] In the structural unit B, R ５ ~R ７ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms, and R ５ and R ６ is preferably a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. ５ and R ６At least one of R is preferably a hydrogen atom. ５ and R ６ It is more preferable that both of the groups are hydrogen atoms.

[0031] In the structural unit B, R ７ may be a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms, but is preferably a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms. ７ When is a monovalent alkyl group having 1 to 20 carbon atoms, the number of carbon atoms in the organic group may be 1 to 15, 1 to 10, 1 to 6, 1 to 5, 1 to 3, or 1. When the alkyl group has 3 or more carbon atoms, it may be a linear, branched, or cyclic hydrocarbon group, and is preferably a linear hydrocarbon group.

[0032] In the structural unit B, Y is a nitrogen atom, an oxygen atom, or a sulfur atom, and may be either a nitrogen atom or an oxygen atom, or may be an oxygen atom.

[0033] In the structural unit B, X ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the divalent functional group is sp ３ It is a hybridized carbon atom. ３ The -Z in the structural unit B is formed by the presence of a hybridized carbon atom. － M ＋ When the divalent functional group has two or more carbon atoms, the mobility of the functional group moiety represented by sp ３ The proportion of hybridized carbon atoms may be, for example, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, based on the total number of carbon atoms being 100. In the case where 100% (i.e., all of the carbon atoms in the organic group are sp ３ The sp in the carbon atom of the divalent functional group may be a hybrid carbon element. ３ The proportion of hybridized carbon atoms can be calculated from the structural formula of the polymer of interest, which is determined by measurements such as NMR and MS.

[0034] In the structural unit B, X ２The number of carbon atoms in the divalent functional group as -Z may be, for example, 2 to 20, 3 to 20, 3 to 15, 3 to 10, 3 to 8, or 4 to 6. When the number of carbon atoms in the divalent functional group is within the above range, -Z － The degree of freedom of movement of the functional group represented by -Z in the polymer is improved. － This promotes the non-uniformity of the distance between the counter ions, M ＋ It will be easier to move around, ＋ When the functional group has 3 or more carbon atoms, it may be a linear or branched hydrocarbon group, and is preferably a linear hydrocarbon group. The hydrocarbon group may be an aliphatic hydrocarbon group. When the divalent functional group is a methylene group (-CH ２ When the divalent functional group has at least one heteroatom (a functional group represented by -, excluding those forming a ring structure) or a heteroatom (a functional group represented by -O-, -S-, etc., excluding those forming a ring structure), the divalent functional group may contain a cyclic hydrocarbon group or an aromatic hydrocarbon group as a partial structure. Some of the carbon atoms constituting the divalent functional group may be substituted with oxygen atoms, and the organic group may be, for example, an oxyalkylene group. The oxyalkylene group may be, for example, an oxymethylene group or an oxyethylene group. The divalent functional group having 1 to 20 carbon atoms, in which at least one of the carbon atoms of the functional group is an sp3 hybridized carbon atom, may specifically be an alkanediyl group or an oxyalkylene group having 1 to 20 carbon atoms.

[0035] The structural unit B may contain at least one of a structural unit represented by the following general formula (B-1) and a structural unit represented by the following general formula (B-2). [In general formula (B-1), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a －is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom. [In general formula (B-2), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom.

[0036] The polymer is a copolymer containing the structural unit A and the structural unit B in a predetermined ratio, but may have structural units other than the structural unit A and the structural unit B. The polymer preferably consists of only the structural unit A and the structural unit B.

[0037] The multiple structural units A present in the polymer may be structural units that independently satisfy the requirements of general formula (A), and the multiple structural units B present in the polymer may be structural units that independently satisfy the requirements of general formula (B). However, from the viewpoint of ease of production, it is desirable that the multiple structural units A present in the polymer be the same structural unit, and it is desirable that the multiple structural units B present in the polymer be the same structural unit. From the viewpoint of improving the mobility of alkali metal ions, the polymer may have a region in which the structural units (A) and the structural units (B) are alternately arranged, and may be an alternating copolymer or a random copolymer. It is preferable that the polymer does not contain a block structure of the structural unit (B).

[0038] In the polymer, the proportion of the structural unit A is 20 to 80% based on all structural units contained in the polymer, but may be, for example, 25 to 75%, 30 to 70%, 35 to 65%, or 40 to 60%.

[0039] In the polymer, the proportion of the structural unit B is 20 to 80% based on all structural units contained in the polymer, but may be, for example, 25 to 75%, 30 to 70%, 35 to 65%, or 40 to 60%.

[0040] In this specification, the ratio of structural units in a polymer (monomer introduction ratio) is the ratio of the number of each structural unit in the polymer to the number of all structural units, and is １ It can be determined by H-NMR measurement.

[0041] The number average molecular weight (Mn) of the polymer may be, for example, 5,000 to 400,000, 8,000 to 300,000, 10,000 to 200,000, or 10,000 to 150,000. The weight average molecular weight (Mw) of the polymer may be, for example, 5,000 to 600,000, 10,000 to 500,000, 20,000 to 400,000, or 20,000 to 300,000. The molecular weight distribution (Mw / Mn) of the polymer may be, for example, 1.0 to 5.0, 1.2 to 3.0, or 1.3 to 2.5.

[0042] The number average molecular weight and weight average molecular weight of the polymer in this specification can be measured by gel permeation chromatography (GPC) performed under the following conditions. For preparing a calibration curve, a standard sample of polymethyl methacrylate (manufactured by Polymer Laboratories, Mn 800 to 2,200,000) is used as the standard substance. <GPC measurement conditions> Apparatus: High-performance liquid chromatograph PU-2080 precision pump RI-2031 refractive-index detector UV-2075 UV / vis detector, manufactured by JASCO Corporation Column: Shodex KF-805L (exclusion limit: 4 × 10 ６ , particle size: 10 μm, pore size: 5000 Å, inner diameter: 0.8 cm, length: 30 cm) Temperature: 40° C. Solvent: dimethylformamide (DMF) Flow rate: 1.0 mL / min Back pressure: 3.0 MPa Detection: RI Sample concentration: 0.5 mass % DMF solution Injection volume: 10 μL

[0043] The polymer may be obtained by polymerization of monomers having polymerizable functional groups corresponding to the structural unit A and the structural unit B. The polymerization method may be, for example, radical polymerization. Examples of the monomer corresponding to the structural unit A include styrene. Examples of the monomer corresponding to the structural unit B include -X ２ -Z － M ＋ Examples thereof include (meth)acrylic acid esters having a partial structure represented by the following formula:

[0044] For example, when the structural unit B is a structural unit represented by the above general formula (B-1) or the above general formula (B-2), a compound represented by the following general formula (b-1) or the following general formula (b-2) can be used as the monomer. In other words, the compound represented by the following general formula (b-1) or the following general formula (b-2) may be a raw material monomer for the above-mentioned polymer according to the present disclosure. Furthermore, the above-mentioned polymer may be a polymer of a monomer composition containing a compound represented by the following general formula (b-1) or the following general formula (b-2). [In general formula (b-1), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom. [In general formula (b-2), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a －is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom.

[0045] The compound represented by the general formula (b-1) or (b-2) can be synthesized inexpensively because the synthesis process can be simplified and the compound can be synthesized from general-purpose raw material compounds, compared to a compound having an alkali metal substituted sulfonylimide group (a compound that is a raw material monomer for the above-mentioned polymer). Therefore, by using the compound represented by the general formula (b-1) or (b-2) as a monomer that provides the structural unit B, the polymer according to the present disclosure can be provided more inexpensively.

[0046] R in the above general formula (b-1) and the above general formula (b-2) ６ ~R ７ , X ２ The above description of the structural unit B can be applied to the structural units Y and M. ８ may be a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms, but is preferably a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms. ７ is a monovalent alkyl group having 1 to 20 carbon atoms, the number of carbon atoms in the organic group may be 1 to 15, 1 to 10, 1 to 6, 1 to 5, 1 to 3, or 1. When the alkyl group has 3 or more carbon atoms, it may be a linear, branched, or cyclic hydrocarbon group, and is preferably a linear hydrocarbon group. The alkyl group may be a halogenated alkyl group. The halogenated alkyl group may be a trifluoromethyl group.

[0047] In the general formula (b-1) and the general formula (b-2), R ６ and R ７ is a hydrogen atom, and R ７ is preferably a methyl group and Y is preferably an oxygen atom, and R ６ and R ７ is a hydrogen atom, and R ７ is a methyl group, and R ８ is a trifluoromethyl group, and X ２It is more preferable that R is a propanediyl group and Y is an oxygen atom. In this case, the compound represented by the general formula (b-1) or (b-2) can be said to be a methacrylate type monomer.

[0048] Electrolyte Composition One embodiment of the electrolyte composition includes the polymer described above.

[0049] The electrolyte composition may contain other components in addition to the polymer. Examples of the other components include organic solvents, alkali metal salts, other resins (binder resins, etc.) such as fluorine-based resins, fabrics such as nonwoven fabrics, porous materials, and viscosity adjusters. The electrolyte composition may contain an organic solvent and an alkali metal salt, or may contain an organic solvent, an alkali metal salt, and a fluorine-based resin.

[0050] (Organic Solvent) Examples of the organic solvent include aprotic solvents. The organic solvent may include one or more solvents selected from the group consisting of carbonate-based solvents, ether-based solvents, fluorine-based solvents, nitrile-based solvents, phosphate-based solvents, and sulfone-based solvents, and may include a carbonate-based solvent.

[0051] Examples of carbonate solvents include chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate (EMC), and cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate. The organic solvent may be a mixed solvent containing two or more carbonate solvents, such as a mixed solvent containing one or more cyclic carbonate solvents and one or more chain carbonate solvents, or a mixed solvent containing two or more cyclic carbonate solvents.

[0052] Examples of ether solvents include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, and 1,3-dioxolane; and chain ethers such as 1,2-diethoxyethane and ethoxymethoxyethane.

[0053] Examples of fluorine-based solvents include hydrofluorocarbons such as perfluorooctane; hydrofluoroethers such as methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether; hydrofluoroolefins such as 1,3,3,3-tetrafluoropropene; and 2,2,2-trifluoro-N,N-dimethylacetamide.

[0054] Examples of the nitrile solvent include acetonitrile, succinonitrile, etc. Examples of the lactone solvent include γ-butyrolactone, etc.

[0055] Examples of phosphate ester solvents include trimethyl phosphate (TMP), triethyl phosphate (TEP), and tris(2,2,2-trifluoroethyl) phosphate (TFEP).

[0056] Examples of sulfonic acid solvents include sulfolane and 3-methylsulfolane.

[0057] Other examples of organic solvents include solvents having a sulfonyl group such as dimethyl sulfoxide (DMSO); amide solvents such as dimethylformamide (DMF) and dimethylacetamide (DMA); organic solvents having a carbonyl group such as acetone (referring to carbonyl compounds other than amide compounds such as -C(=O)-, esters, ketones, and aldehydes); and nitrogen-containing aromatic compounds such as pyridine (compounds containing nitrogen as a ring member of the aromatic ring, which may be either a monocyclic or fused ring system). Only one organic solvent may be used, or a mixed solvent containing two or more organic solvents may be used.

[0058] The content of the organic solvent may be, for example, 10 to 1000 parts by mass, 50 to 800 parts by mass, 100 to 600 parts by mass, 150 to 600 parts by mass, or 200 to 500 parts by mass relative to 100 parts by mass of the polymer contained in the electrolyte composition.

[0059] (Alkali Metal Salt) Examples of the alkali metal salt include MF, MCl, MBr, MI, and MNO, where M is an alkali metal. ３ , MClO ４ , MPF ６ , MBF４ , M ２ SO ４ , M[(C ｈ F ２ｈ＋１ ) SO ３ ] (h is 0 to 3), M[(C ｈ F ２ｈ＋１ ) SO ２ ] ２ N (h is 0 to 3), M{[(C ｈ F ２ｈ＋１ ) SO ２ ]N[(C ｉ F ２ｉ＋１ ) SO ２ ]} (h and i are 0 to 3), and MBOB (BOB is bisoxalatoborate). The alkali metal salt may be used alone or in combination of two or more. The alkali metal M is not particularly limited as long as it is an element classified as an alkali metal, and may contain, for example, lithium, sodium, or potassium, or may contain lithium or sodium, or may contain lithium. The alkali metal salt may be a lithium salt compound. Specific examples of the lithium salt compound include lithium bis(trifluoromethanesulfonyl)imide, lithium triflimide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiPHF), and lithium hexafluorophosphate (LiPF ６ The alkali metal element contained in the alkali metal salt may be the same as the alkali metal element in the structural unit B contained in the polymer.

[0060] The content of the alkali metal salt in the electrolyte composition may be, for example, 0.1 to 200 mol %, 2.5 to 150 mol %, 5 to 100 mol %, or 10 to 60 mol % in terms of the alkali metal ions contained in the alkali metal salt relative to the total amount of the structural unit B contained in the polymer.

[0061] The content of the lithium salt compound may be, for example, 0.05 to 3.0 equivalents, 0.1 to 2.5 equivalents, 0.2 to 2.0 equivalents, or 0.5 to 1.5 equivalents relative to 1 equivalent of the substance amount of lithium ions in the polymer.

[0062] (Fluorine-based resin) The fluorine-based resin may include a resin having a carbon chain as the main chain. The carbon chain may be formed by radical polymerization of an ethylenically unsaturated group. Examples of fluorine-based resins include polytetrafluoroethylene (PTFE), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and polyvinylidene fluoride (PVDF). When the electrolyte composition contains a carbonate-based solvent, the fluorine-based resin may function as a gelling agent. When the electrolyte composition contains a carbonate-based solvent and a fluorine-based resin, the handleability of the electrolyte composition can be further improved.

[0063] The content of the fluororesin may be 10 to 200 parts by mass, or 50 to 150 parts by mass, relative to 100 parts by mass of the polymer. The content of the fluororesin may be, for example, 0.1 to 20% by mass, 0.1 to 10% by mass, or 0.1 to 5% by mass, relative to the total amount of the electrolyte composition.

[0064] An example of a method for producing an electrolyte composition includes mixing a polymer and an organic solvent. At this time, other components such as an alkali metal salt and a fluorine-based resin may be added. The electrolyte composition may be formed into a film or pellets and used as a molded product.

[0065] The electrolyte composition of this embodiment can be used, for example, as a composition for forming an electrolyte in a battery, a capacitor, or the like. That is, one embodiment of a battery or capacitor has an electrolyte, and the electrolyte may include the above-described electrolyte composition. Examples of the battery include batteries that charge and discharge by the movement of alkali metal ions, such as lithium ion batteries and sodium ion batteries. The battery may be a primary battery, a secondary battery, or a solid-state battery. The electrolyte composition of this embodiment may be used as an electrode material and may be contained in at least one of the positive electrode and the negative electrode.

[0066] [Battery] One embodiment of a battery includes the above-described polymer or the above-described electrolyte composition. The battery of this embodiment includes a positive electrode, a negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode, and the electrolyte may include the above-described polymer or the above-described electrolyte composition. The electrolyte may be formed by disposing the polymer or the electrolyte composition of this embodiment between the positive electrode and the negative electrode.

[0067] The positive electrode may be a layer containing a positive electrode material formed on a current collector, and the negative electrode may be a layer containing a negative electrode material formed on a current collector.

[0068] Furthermore, when the electrolyte composition contains an organic solvent, an interface can be more easily formed between the electrodes (positive electrode and negative electrode) and the electrolyte. In other words, the electrolyte composition may contain an organic solvent to form an interface between at least one of the positive electrode and the electrolyte and the negative electrode and the electrolyte. Hereinafter, the battery according to this embodiment will be described using a lithium ion battery as an example.

[0069] The positive electrode includes a positive electrode active material. The positive electrode active material is not particularly limited, and examples thereof include lithium composite metal oxides containing lithium and a transition metal element. The transition metal element may be at least one element selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Cu, and Al, and may contain Ni. Examples of lithium composite metal oxides include LiCoO ２ , LiNiO ２ , LiMn ２ O ４ , LiNi ０．５ Mn １．５ O ４ , Li ２ MnO ３ , LiNi ｘ Mn ｙ Co １－ｘ－ｙ O ２ [0<x+y<1]), LiNi ｘ Co ｙ Al １－ｘ－ｙ O ２ [0<x+y<1]), LiCr ０．５ Mn ０．５ O ２ , LiFePO ４ , Li２ FeP ２ O ７ , LiMnPO ４ , LiFeBO ３ , Li ３ V ２ (P.O. ４ ) ３ , Li ２ CuO ２ , Li ２ FeSiO ４ , and Li ２ MnSiO ４ When the positive electrode active material contains an alkali metal element other than Li, specific examples thereof include those in which Li in the above specific examples is replaced with another alkali metal.

[0070] The positive electrode may contain, for example, a conductive additive, a binding resin (binder), and the like, as needed.

[0071] The negative electrode includes a negative electrode active material, such as a simple element such as Li, Si, P, Sn, Si—Mn, Si—Co, Si—Ni, In, or Au, an alloy or composite containing these elements, a carbon material such as graphite, a substance in which lithium ions are inserted between layers of the carbon material, or an oxide containing titanium.

[0072] The negative electrode may contain, for example, a conductive additive, a binding resin (binder), and the like, as needed.

[0073] The battery may have a separator. The separator may be, for example, a porous material. The porous material may be, for example, a resin porous material. Specific examples of resin porous materials include porous polyolefin membranes and porous ceramic membranes.

[0074] Although several embodiments have been described above, the present disclosure is not limited to the above embodiments. Furthermore, the descriptions of the above embodiments can be applied to each other.

[0075] The present disclosure will be described in more detail below using examples and comparative examples, but the present disclosure is not limited to the following examples.

[0076] [Synthesis of Monomer X] Monomer X represented by the following formula (X) was synthesized by the following method.

[0077]

[0078] A reactor equipped with a cooler and a stirrer was charged with 20.0 g (81.2 mmol) of potassium 3-sulfopropyl methacrylate and 34 mL of tetrahydrofuran, and after adding 2.0 mL of N,N-dimethylformamide, 36.8 mL (406 mmol) of thionyl chloride was added dropwise in an ice bath. After stirring for 1 hour in the ice bath and overnight at room temperature, 340 mL of ice water was slowly added to the reaction solution. The reaction solution was extracted with 120 mL of dichloromethane, and the organic layer was washed four times with 40 mL of water and dried over magnesium sulfate. The organic layer was separated, and the solvent in the organic layer was distilled off under reduced pressure to obtain 18.3 g (yield 97%) of 3-(chlorosulfonyl)propyl methacrylate as a colorless, transparent oil.

[0079] Next, 3.0 g (20.0 mmol) of trifluoromethanesulfonamide and 16 mL of anhydrous tetrahydrofuran were placed in a reactor equipped with a cooler and a stirrer, and 5.9 mL (42 mmol) of triethylamine was added. After cooling to 0°C, a solution of 4.6 g (20.0 mmol) of 3-(chlorosulfonyl)propyl methacrylate synthesized as described above in 6 mL of anhydrous tetrahydrofuran was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the precipitate was removed by filtration, and the solvent was then distilled off under reduced pressure. 40 mL of dichloromethane was added to the residue, and the organic layer was washed four times with 16 mL of water and then dried over anhydrous magnesium sulfate. The organic layer was separated, the solvent in the organic layer was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: chloroform / methanol=10 / 1) to obtain 4.8 g (yield 54%) of triethylammonium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide as a brown oil.

[0080] Next, 4.8 g (10.8 mmol) of triethylammonium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide synthesized as described above and 5 mL of tetrahydrofuran were placed in a reactor equipped with a cooler and a stirrer, and 0.2 g (27 mmol) of lithium hydride was added. The reactor was maintained at 30°C and stirred for about 10 hours, and then stirred at room temperature overnight. The precipitate was removed by filtration, and the solvent was distilled off under reduced pressure. Hexane was added to the residue, and decantation was carried out three times. The residue was dried under reduced pressure to obtain 3.5 g (yield 93%) of monomer X as a light brown solid. Monomer X was characterized by proton nuclear magnetic resonance ( １ The structure was identified by 1 H-NMR spectroscopy.

[0081] [Synthesis of Monomer Y] Monomer Y represented by the following formula (Y) was synthesized by the following method.

[0082]

[0083] A reactor equipped with a cooler and a stirrer was charged with 15.0 g (64.5 mmol) of 3-sulfopropyl potassium acrylate and 26 mL of tetrahydrofuran. After adding 1.5 mL of N,N-dimethylformamide, 32.2 mL (355 mmol) of thionyl chloride was added dropwise in an ice bath. After stirring for 1 hour in the ice bath and overnight at room temperature, 240 mL of ice water was slowly added to the reaction solution. The reaction solution was extracted with 100 mL of dichloromethane, and the organic layer was washed four times with 50 mL of water and dried over magnesium sulfate. The organic layer was separated, and the solvent in the organic layer was distilled off under reduced pressure. Purification by silica gel chromatography (developing solvent: hexane / ethyl acetate = 3 / 1) afforded 7.7 g of 3-(chlorosulfonyl)propyl acrylate (yield: 56%).

[0084] Next, 2.0 g (13.4 mmol) of trifluoromethanesulfonamide and 10 mL of anhydrous tetrahydrofuran were placed in a reactor equipped with a cooler and a stirrer, and 3.9 mL (28 mmol) of triethylamine was added. After cooling to 0°C, a 10 mL solution of 2.8 g (13.4 mmol) of 3-(chlorosulfonyl)propyl acrylate synthesized as described above in tetrahydrofuran was added dropwise. After the dropwise addition, the mixture was stirred at 0°C for 1 hour and at room temperature for 1 hour, and then the precipitate was removed by filtration. The solvent was distilled off from the resulting solution under reduced pressure. 40 mL of dichloromethane was added to the residue, and the organic layer was washed four times with 16 mL of water and then dried over anhydrous magnesium sulfate. The organic layer was separated, the solvent in the organic layer was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: chloroform / methanol=10 / 1) to obtain 1.6 g (yield 27%) of triethylammonium 1-[3-(acryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide as a brown oil.

[0085] Next, 1.6 g (3.7 mmol) of triethylammonium 1-[3-(acryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl)imide synthesized as described above and 3 mL of tetrahydrofuran were placed in a reactor equipped with a cooler and a stirrer, and 0.073 g (9.2 mmol) of lithium hydride was added. The reactor was maintained at 30°C and stirred for about 7 hours, and then stirred at room temperature overnight. After filtering off the precipitate, the solvent was distilled off from the solution under reduced pressure, and the residue was decanted twice with hexane and twice with dichloromethane. The residue was dried under reduced pressure to obtain 1.0 g of monomer Y (yield 82%). Monomer Y was characterized by proton nuclear magnetic resonance ( １ The structure was identified by H-NMR spectral analysis.

[0086] [Synthesis of Monomer P] Monomer P represented by the following formula (P) was synthesized by the following method.

[0087]

[0088] Under a nitrogen atmosphere, benzenesulfonamide (Tokyo Chemical Industry Co., Ltd., 4.45 g, 28.3 mmol) and triethylamine (Tokyo Chemical Industry Co., Ltd., 6.24 g, 61.7 mmol) were added to anhydrous tetrahydrofuran (23 mL, Kanto Chemical Co., Ltd.) to prepare a solution. After cooling this solution to 0°C, a solution of 3-(chlorosulfonyl)propyl methacrylate (6.42 g, 28.3 mmol) in anhydrous tetrahydrofuran (9 mL) was added, and the reaction was carried out for 2 hours. After the temperature of the reaction solution was returned to room temperature, it was filtered, and the solvent was distilled off from the filtrate under reduced pressure. The residue was dissolved in dichloromethane and washed four times with ion-exchanged water, after which magnesium sulfate was added and the mixture was allowed to stand for 30 minutes. The magnesium sulfate was filtered, and a trace amount of dibutylhydroxytoluene was added to the filtrate, and the solvent was distilled off under reduced pressure. As a result, 8.25 g (yield 65%) of an intermediate represented by the following formula (P-1) was obtained. The resulting intermediate was a yellow oily solid.

[0089]

[0090] Under a nitrogen atmosphere, the intermediate (8.25 g, 18.4 mmol) synthesized as described above was dissolved in anhydrous tetrahydrofuran (25 mL) and cooled to 0°C. A mixture of lithium hydride (manufactured by Aldrich, 0.22 g, 27.6 mmol) and anhydrous tetrahydrofuran (13 mL) was then added and the reaction was carried out for 2 hours. The reaction solution was returned to room temperature, filtered, and a trace amount of dibutylhydroxytoluene was added to the filtrate, after which the solvent was distilled off under reduced pressure. After drying under reduced pressure, 6.5 g (yield 100%) of monomer P was obtained as a yellow oily solid. [Synthesis of Monomer Q] Monomer Q represented by the following formula (Q) was synthesized by the following method.

[0091]

[0092] Under a nitrogen atmosphere, lithium hydride (manufactured by Aldrich, 0.47 g, 59.4 mmol) was added to anhydrous tetrahydrofuran (13 mL, manufactured by Kanto Chemical Co., Ltd.) to prepare a mixed solution. To this mixed solution, a solution of trifluoroacetamide (manufactured by Tokyo Chemical Industry Co., Ltd., 3.20 g, 28.3 mmol) dissolved in anhydrous tetrahydrofuran (13 mL) was added at 0 ° C., and after addition, the mixture was warmed to room temperature and reacted for 1 hour. Thereafter, the mixture was cooled again to 0 ° C., and a solution of 3-(chlorosulfonyl)propyl methacrylate (6.42 g, 28.3 mmol) in anhydrous tetrahydrofuran (13 mL) was added. After reacting for 1 hour, the temperature of the reaction solution was returned to room temperature, filtered, and the solvent was distilled off from the filtrate under reduced pressure. The residue was decanted with dichloromethane containing a trace amount of dibutylhydroxytoluene and dried under reduced pressure, resulting in 6.5 g (75% yield) of monomer Q as a pale yellow oily solid.

[0093] (Example 1-1) [Synthesis of Polymer 1] 0.69 g of the monomer X obtained as described above, 0.23 mL of styrene, and 6.6 mg of azobisisobutyronitrile were dissolved in 1.4 mL of dehydrated N,N-dimethylformamide, and the reaction was carried out for 24 hours at 60°C under a nitrogen atmosphere while checking the monomer consumption rate using the solvent as an internal standard. The polymerized solution was dialyzed in methanol, and the solution in the dialysis membrane was distilled off using an evaporator at room temperature. The polymer was dissolved in 30 mL of water, freeze-dried, and then further vacuum-dried at 80°C to obtain 0.58 g (yield 77%) of a copolymer (hereinafter also referred to as polymer 1). The monomer introduction ratio was monomer X:styrene = 50.5:49.5. The monomer introduction ratio of the copolymer was １ The copolymer had a number average molecular weight Mn of 183,000, a weight average molecular weight Mw of 333,000, and a molecular weight distribution Mw / Mn of 1.82. The number average molecular weight and weight average molecular weight were measured by gel permeation chromatography.

[0094] (Example 1-2) [Synthesis of Polymer 2] 0.21 g of the methacrylate-type monomer X obtained as described above, 0.16 mL of styrene, and 3.3 mg of azobisisobutyronitrile were dissolved in 0.74 mL of dehydrated N,N-dimethylformamide, and the mixture was reacted for 24 hours at 60°C under a nitrogen atmosphere while checking the monomer consumption rate using the solvent as an internal standard. The polymerized solution was dialyzed in methanol, and the solution in the dialysis membrane was distilled off using an evaporator at room temperature. The resulting solution was dissolved in 30 mL of water, freeze-dried, and then further vacuum-dried at 80°C to obtain 0.20 g (80% yield) of a copolymer (hereinafter also referred to as polymer 2). The monomer introduction ratio was monomer X:styrene = 31.8:68.2. The monomer introduction ratio of the copolymer was １ The number average molecular weight Mn of the copolymer was 230,000, the weight average molecular weight Mw of the copolymer was 451,000, and the molecular weight distribution Mw / Mn of the copolymer was 1.96. The number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography.

[0095] (Example 1-3) [Synthesis of Polymer 3] 0.67 g of acrylate-type monomer Y, 0.23 mL of styrene, and 6.6 mg of azobisisobutyronitrile were dissolved in 1.4 mL of dehydrated N,N-dimethylformamide, and the reaction was carried out for 24 hours at 60°C under a nitrogen atmosphere while checking the monomer consumption rate using the solvent as an internal standard. The polymerized solution was dialyzed in methanol, and the solution in the dialysis membrane was distilled off using an evaporator at room temperature. The solution was dissolved in 30 mL of water, freeze-dried, and then further vacuum-dried at 80°C to obtain 0.42 g (yield 75%) of a copolymer (hereinafter also referred to as polymer 3). The monomer introduction ratio was monomer Y:styrene = 50.7:49.3. The monomer introduction ratio of the copolymer was １ The number average molecular weight Mn of the copolymer was 143,000, the weight average molecular weight Mw of the copolymer was 222,000, and the molecular weight distribution Mw / Mn of the copolymer was 1.55. The number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography.

[0096] (Example 1-5) [Synthesis of Polymer 5] 0.88 g of methacrylate-type monomer P, 0.29 mL of styrene, and 8.2 mg of azobisisobutyronitrile were dissolved in dehydrated N,N-dimethylformamide to a total volume of 5 mL. After 24 hours of reaction at 60°C under a nitrogen atmosphere while monitoring the monomer consumption rate using the solvent as an internal standard, the reaction solution was dialyzed against distilled water. The dialyzed aqueous solution was lyophilized and then further vacuum-dried at 60°C to obtain 0.72 g (63% yield) of a copolymer (hereinafter also referred to as Polymer 2). The monomer incorporation ratio was monomer Y:styrene = 46.2:52.8. The monomer incorporation ratio was calculated from 1H-NMR of the copolymer. The copolymer had a number-average molecular weight Mn of 97,000, a weight-average molecular weight Mw of 147,000, and a molecular weight distribution Mw / Mn of 1.52. The number average molecular weight and weight average molecular weight were measured by gel permeation chromatography.

[0097] Example 1-6 [Synthesis of Polymer 6] 3.09 g of methacrylate-type monomer Q, 1.14 mL of styrene, and 32.8 mg of azobisisobutyronitrile were dissolved in dehydrated N,N-dimethylformamide to a total volume of 20 mL. After 24 hours of reaction at 60°C under a nitrogen atmosphere while monitoring the monomer consumption rate using the solvent as an internal standard, the reaction solution was dialyzed against distilled water. The dialyzed aqueous solution was lyophilized and then further vacuum-dried at 60°C to obtain 1.69 g (41% yield) of a copolymer (hereinafter also referred to as Polymer 3). The monomer incorporation ratio was monomer Z:styrene = 41.2:58.8. The monomer incorporation ratio was calculated from 1H-NMR of the copolymer. The copolymer had a number-average molecular weight Mn of 69,000, a weight-average molecular weight Mw of 133,000, and a molecular weight distribution Mw / Mn of 1.93. The number average molecular weight and weight average molecular weight were measured by gel permeation chromatography.

[0098] Example 1 [Production of Electrolyte Composition] A resin mixture of 100 parts by mass of the polymer 1 and 50 parts by mass of PVdF-HFP (poly(vinylidene fluoride-co-hexafluoropropylene)) was mixed with 300 parts by mass of an organic solvent to prepare a gel electrolyte composition. The organic solvent used was a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1).

[0099] Example 2 [Production of Electrolyte Composition] An electrolyte composition was prepared in the same manner as in Example 1, except that the organic solvent used in preparing the electrolyte composition was a mixture of a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1) and fluoroethylene carbonate (FEC) in a mass ratio of 95:5, and that lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was added in an amount equivalent to 20 mol % of the lithium ions contained in LiTFSI relative to 100 mol % of the structure derived from monomer X contained in the copolymer (corresponding to structural unit B).

[0100] Examples 3 to 12 [Production of Electrolyte Compositions] Electrolyte compositions were prepared in the same manner as in Example 2, except that the components and blending amounts were changed as shown in Table 1.

[0101] Examples 13 to 16 [Production of Electrolyte Compositions] Electrolyte compositions were prepared in the same manner as in Example 2, except that the components and blending amounts were changed as shown in Table 2. In Table 2, EMC represents ethyl methyl carbonate, and LiPF6 represents lithium hexafluorophosphate.

[0102] Comparative Example 1 Synthesis of Monomer Z Monomer Z represented by the following formula (Z) was synthesized by the following method.

[0103]

[0104] First, N-phenylmaleimide (30 g, 0.17 mol) and chlorosulfonic acid (69 mL, 1.04 mol) were added to a reactor at 0°C and stirred at 45-50°C for 1 hour. The resulting product was cooled to room temperature and poured onto ice. After stirring for a while, the precipitated crystals were collected by filtration and purified by silica gel column chromatography. The eluent used was a mixture of hexane and ethyl acetate in a volume ratio of 2 / 1 to 1 / 1. As a result of purification, 34 g (yield 73%) of an intermediate represented by the following formula was obtained. The resulting intermediate was a pale yellow solid.

[0105]

[0106] Next, under a nitrogen atmosphere, trifluoromethanesulfonamide (manufactured by Tokyo Chemical Industry Co., Ltd.) (4.22 g, 28.3 mmol) was dissolved in dehydrated acetonitrile (120 mL, manufactured by Kanto Chemical Co., Ltd.) to prepare a solution. To this solution, 1.0 equivalent of lithium carbonate (2.09 g, 28.3 mmol) relative to trifluoromethanesulfonamide, 2.0 equivalents of lithium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.36 g, 56.6 mmol), and the intermediate synthesized as described above (7.00 g, 25.8 mmol) were added in that order, and the reaction was carried out at 0 ° C. for 4.5 hours. After the temperature of the reaction solution was returned to room temperature, it was filtered, and the solvent was distilled off from the filtrate under reduced pressure. The residue was decanted with diethyl ether and dried under reduced pressure, yielding 10.5 g of monomer Z as a pale brown solid.

[0107] [Synthesis of Polymer 4] 0.558 g of maleimide-type monomer Z, 0.149 g of styrene, and 11.7 mg of azobisisobutyronitrile were dissolved in 6.7 mL of dehydrated acetonitrile, and the monomer consumption rate was confirmed by adding tetralin as an internal standard substance. The reaction was carried out at 60°C for 24 hours under a nitrogen atmosphere. The polymerization solution was dialyzed in acetonitrile and vacuum dried at 120°C to obtain 0.640 g of copolymer (yield 87%). The monomer introduction ratio was monomer Z:styrene = 52:48. １ The number average molecular weight of the copolymer was calculated from H-NMR. Mn = 9.4 × 10 ４ , weight average molecular weight Mw=4.2×10 ５The number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography.

[0108] [Production of Electrolyte Composition] Electrolyte compositions were prepared in the same manner as in Example 2, except that the components and their amounts were changed as shown in Table 1.

[0109] Reference Example 1 [Production of Electrolyte Composition] A gel-like electrolyte composition was prepared by mixing 100 parts by mass of polyethylene oxide (PEO), 200 parts by mass of an organic solvent, and 5 mol% of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) relative to 100 mol% of the ethylene oxide unit of PEO. The organic solvent used was a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) (volume ratio 1:1).

[0110] <Measurement of ionic conductivity σ> An evaluation cell of coin-type battery CR2032 was assembled in a glove box under a dry argon atmosphere. Specifically, first, each layer was laminated in the evaluation cell in the following order: stainless steel plate / electrolyte composition layer / stainless steel plate to prepare a test laminate B. Hereinafter, the evaluation cell including the test laminate B will be referred to as evaluation cell B.

[0111] Impedance measurement was performed on the evaluation cell B using an impedance measuring device under the conditions of 25°C, a frequency range of 0.1 Hz to 1 MHz, and an applied voltage of 10 mV (vs. open circuit voltage). The ionic conductivity σ was calculated using the following formula. In the formula, R represents the impedance value, A represents the area of ​​the electrolyte composition layer, and t represents the thickness of the electrolyte composition layer. The results are shown in Tables 1 and 2. σ (S cm －１ )=t(cm) / (R(Ω)×A(cm ２ ))

[0112] <Measurement of Activation Energy Ea> Ion conductivity measurements using the above-mentioned evaluation cell B were also carried out under conditions of 30°C, 40°C, 50°C, 60°C, and 70°C, and changes in ionic conductivity with respect to temperature were measured. Activation energy was calculated from the slope of a graph of the common logarithm of ionic conductivity versus the reciprocal of temperature using the Arrhenius equation (log k = log A - Ea / RT, where k is the reaction rate constant, A is the frequency factor, Ea is the activation energy, R is the gas constant, and T is the absolute temperature). The results are shown in Tables 1 and 2.

[0113] <Measurement of Lithium Ion Transference Number> An evaluation cell of a coin-type battery CR2032 was assembled in a glove box under a dry argon atmosphere. Specifically, first, layers were stacked in the evaluation cell in the order of lithium / electrolyte composition / lithium to prepare a test laminate A. Hereinafter, the evaluation cell including the test laminate A will be referred to as evaluation cell A.

[0114] The lithium ion transport number was measured for the evaluation cell A. The lithium ion transport number was measured by first applying 10 mV to the evaluation cell A at room temperature (25° C.) and measuring the initial current value (I ０ ) and steady-state current value (I ｓｓ Next, the lithium ion transport number (t Ｌｉ＋ The results are shown in Tables 1 and 2. Ｌｉ＋ =I ｓｓ / I ０

[0115] <Measurement of Maximum DC Current Density> The maximum DC current density was measured for each of the electrolyte compositions prepared in Examples 1 to 15 and Comparative Example 1 according to the following method. The results are shown in Tables 1 and 2. In Tables 1 and 2, "-" indicates that no measurement was performed. Graphs showing the evaluation results of DC current density for evaluation cells using the electrolyte compositions of Example 1 and Reference Example 1 are shown in FIGS. 1 and 2.

[0116] In Examples 1, 11, and 12, the evaluation cell A was alternately supplied with 0.02 mA / cm 2 in the positive and negative directions. ２ , 0.1mA / cm ２ , 0.2mA / cm ２ , 0.3mA / cm２ , 0.4mA / cm ２ , 0.5mA / cm ２ , 0.6mA / cm ２ , 0.7mA / cm ２ , 0.8mA / cm ２ , 0.9mA / cm ２ , 1.0mA / cm ２ , 1.1mA / cm ２ , and 1.2 mA / cm ２ A constant current test was carried out in which current densities of 1.0 V and 2.0 V were applied in this order for five cycles, and the test was terminated when the voltage reached 1.5 V. The maximum current density that could be applied before the voltage reached 1.5 V was defined as the maximum DC current density.

[0117] In Examples 2 to 10 and Examples 13 to 15, a current of 0.02 mA / cm was applied alternately to the evaluation cell A in the positive and negative directions. ２ , 0.1mA / cm ２ , 0.2mA / cm ２ , 0.4mA / cm ２ , 0.8mA / cm ２ , 1.2mA / cm ２ , 1.6mA / cm ２ , 2.0mA / cm ２ , 2.4mA / cm ２ , 2.8mA / cm ２ , 3.2mA / cm ２ , 3.6mA / cm ２ , 4.0mA / cm ２ , and 4.4 mA / cm ２ A constant current test was carried out in which current densities of 1.0 V and 2.0 V were applied in this order for five cycles, and the test was terminated when the voltage reached 1.5 V. The maximum current density that could be applied before the voltage reached 1.5 V was defined as the maximum DC current density.

[0118] In Reference Example 1, the evaluation cell A was alternately supplied with 0.02 mA / cm 2 in the positive and negative directions. ２ , 0.1mA / cm ２ , 0.2mA / cm ２ , 0.4mA / cm ２ , 0.6mA / cm ２ , 0.8mA / cm ２ , 1.0mA / cm ２, 1.2mA / cm ２ , 1.4mA / cm ２ , 1.6mA / cm ２ , 1.8mA / cm ２ , 2.0mA / cm ２ A constant current test was carried out by applying 5 cycles of DC current, 1.0 V, and 2.0 V in this order, and the test was terminated when the voltage reached 1.5 V. The maximum current density that could be applied before the voltage reached 1.5 V was defined as the maximum DC current density.

[0119]

[0120]

[0121] As shown in Table 1, the electrolyte composition of Reference Example 1, which used PEO as the polymer, was excellent in terms of ionic conductivity, but had a low Li-ion transport number, and it was confirmed that the maximum DC current density was not sufficiently high. In contrast, it was confirmed that the electrolyte composition using Polymer 4, in which an anionic functional group ionized with an alkali metal was introduced into the main chain of the polymer, and the electrolyte compositions of Examples, which used Polymers 1 to 3, which satisfy the requirements of the polymer according to the present disclosure, were significantly superior in terms of Li-ion transport number. Furthermore, it was confirmed that the electrolyte compositions of Examples were also superior in terms of maximum DC current density compared to the electrolyte composition of Reference Example, and were useful as polymer electrolytes.

[0122] Furthermore, in the structure corresponding to general formula (B), -X ２ When comparing Polymer 1 and Polymer 4, which differ in the presence or absence of a functional group represented by -, that is, the results of the electrolyte compositions of Examples 3 and 4 and the electrolyte compositions of Comparative Examples 1 and 2, it is clear that -X ２ It was confirmed that the introduction of a functional group represented by - further improved ionic conductivity.

[0123] According to the present disclosure, a novel polymer usable as a polymer electrolyte can be provided. According to the present disclosure, an electrolyte composition and a battery containing the polymer can also be provided. According to the present disclosure, a novel compound having an alkali metal-substituted carbonylsulfonylimide group can also be provided.

Claims

1. A polymer comprising a structural unit A represented by the following general formula (A) and a structural unit B represented by the following general formula (B), wherein the proportion of the structural unit A is 20 to 80% and the proportion of the structural unit B is 20 to 80% based on the total structural units contained in the polymer. [In general formula (A), R １ ~R ４ are each independently a hydrogen atom, a halogen atom, a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent aryl group having 1 to 20 carbon atoms; １ represents an oxygen atom, a divalent alkanediyl group having 1 to 20 carbon atoms, or a divalent arylene group having 1 to 20 carbon atoms, and —CH ２ A part of the - group may be substituted with -O-, -NH-, -(C═O)-, -(C═O)-O-, -O-(C═O)-, -(C═O)-NH-, or -NH-(C═O)-.] [In general formula (B), R ５ ~R ７ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom.

2. The polymer according to claim 1, wherein in the structural unit B, M is a lithium atom or a sodium atom.

3. -Z in the structural unit B － M ＋ 2. The polymer according to claim 1, wherein the partial structure represented by the formula: is a functional group selected from the group consisting of a lithiated sulfonic acid group, a lithiated carboxy group, a lithiated sulfonylimide group, and a lithiated carbonylsulfonylimide group.

4. The polymer according to claim 1, wherein the structural unit B comprises at least one of a structural unit represented by the following general formula (B-1) and a structural unit represented by the following general formula (B-2): [In general formula (B-1), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom. [In general formula (B-2), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom.

5. The polymer according to claim 1, which is an alternating copolymer or a random copolymer, and which comprises the structural unit A and the structural unit B.

6. An electrolyte composition comprising the polymer according to any one of claims 1 to 5.

7. The electrolyte composition of claim 6, further comprising an organic solvent.

8. The electrolyte composition of claim 6, further comprising an alkali metal salt.

9. The electrolyte composition of claim 6, further comprising an organic solvent and an alkali metal salt.

10. A battery comprising the electrolyte composition of claim 6.

11. A compound represented by the following general formula (b-1) or the following general formula (b-2): [In general formula (b-1), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom. [In general formula (b-2), R ５ ~R ８ are each independently a hydrogen atom, a halogen atom, or a monovalent alkyl group having 1 to 20 carbon atoms; ２ is a divalent functional group having 1 to 20 carbon atoms, and at least one of the carbon atoms of the functional group is sp ３ Y is a nitrogen atom, an oxygen atom, or a sulfur atom; Z is a － is an anionic functional group, and M is a lithium atom, a sodium atom, or a potassium atom.

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