Electrolyte solution for nonaqueous sodium-ion battery, nonaqueous sodium-ion battery, and method

Abstract

The present disclosure provides: an electrolyte solution for a non-aqueous sodium-ion battery, the non-aqueous sodium-ion battery, and a method for manufacturing the non-aqueous sodium-ion battery, the electrolyte solution for a non-aqueous sodium-ion battery comprising: (I) a fluorine sulfate; (II) at least one compound selected from the group consisting of a compound having at least two isocyanate groups, a compound represented by a specific general formula (1), a compound represented by a specific general formula (2), and a compound represented by a specific general formula (5); (III) a sodium salt; and (IV) a non-aqueous solvent. The non-aqueous sodium-ion battery is provided with at least a positive electrode, a negative electrode, and the electrolyte solution for non-aqueous sodium-ion batteries.

Description

Technical Field

[0001] One embodiment of the present disclosure relates to: an electrolyte for a non-aqueous sodium ion battery, a non-aqueous sodium ion battery using the same, and a method for manufacturing a non-aqueous sodium ion battery. Background Art

[0002] In recent years, lithium ion batteries have attracted attention as small, high energy density storage systems for information-related devices, communication devices, namely personal computers, digital video cameras, digital still cameras, mobile phones, etc.; and large, power-oriented storage systems for electric vehicles, hybrid vehicles, fuel cell vehicle auxiliary power supplies, power storage, etc. On the other hand, the price of lithium has risen, and cheaper sodium ion batteries have attracted attention as next-generation secondary batteries (Patent Document 1).

[0003] Proposals have been made to suppress deterioration caused by decomposition of the electrolyte on the surfaces of the positive and negative electrodes of a non-aqueous sodium ion battery using various additives. Patent Document 2 discloses a non-aqueous electrolyte for a sodium secondary battery that improves charge-discharge cycle characteristics by containing a sulfonate compound (e.g., methylene bis(benzenesulfonate), methylene bis(2-trifluoromethylbenzenesulfonate), methyl benzenesulfonate), a sulfoxide compound (e.g., dimethyl sulfoxide), etc., having a -(S=O)- bond.

[0004] On the other hand, Patent Documents 3 and 4 disclose that if fluorosulfate is added to a non-aqueous lithium ion battery electrolyte, high-temperature durability and power characteristics are improved.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2013-48077

[0008] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2016-181467

[0009] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2011-187440

[0010] Patent Document 4: International Publication No. 2018 / 179884 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] Although non-aqueous sodium ion batteries have started to be put into practical use, the results of the research by the present inventors have determined that there is room for improvement in, for example, cycle characteristics, gas generation amount (inhibiting effect) in a high-temperature cycle test, and high-temperature storage characteristics for applications used in places such as in automobiles for a long time at high temperatures.

[0013] Therefore, one of the problems of one embodiment of the present disclosure is to provide an electrolyte for a non-aqueous sodium-ion battery, a non-aqueous sodium-ion battery using the same, and a method for manufacturing a non-aqueous sodium-ion battery, which can improve at least one of the cycle characteristics at a temperature of 60 °C or higher, the amount of gas generated (inhibiting effect) in a high-temperature cycle test, and the high-temperature storage characteristics of the non-aqueous sodium-ion battery.

[0014] Means for solving the problems

[0015] In view of the above problems, the present inventors conducted in-depth research and found that: by including (I) fluorosulfate; (II) at least one selected from the group consisting of a compound having at least two isocyanate groups, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (5); (III) sodium salt; and (IV) a non-aqueous solvent, an electrolyte for a non-aqueous sodium-ion battery can be obtained, which can improve at least one of the cycle characteristics at a temperature of 60 °C or higher, the amount of gas generated (inhibiting effect) in a high-temperature cycle test, and the high-temperature storage characteristics of the non-aqueous sodium-ion battery. Thus, the present disclosure was completed.

[0016] That is, the present disclosure includes the following embodiments. [1]

[0018] An electrolyte for a non-aqueous sodium-ion battery, comprising:

[0019] (I) fluorosulfate;

[0020] (II) at least one selected from the group consisting of a compound having at least two isocyanate groups, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (5);

[0021] (III) sodium salt; and,

[0022] (IV) a non-aqueous solvent.

[0023]

[0024] [In the general formula (1), n represents an integer of 1 to 4.

[0025] R 1 and R 2Each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.

[0026] Y 1 and Y 2 Each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or -O - (M 1 A+ ) a ,M 1 A+ represents a proton, a metal cation or an onium cation, A represents the valence of the cation. a represents a number such that A×a = 1.

[0027]

[0028] [In general formula (2), R 3 represents a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or -O - (M 2 B+ ) b ,M 2 B+ represents a proton, a metal cation or an onium cation, B represents the valence of the cation. b represents a number such that B×b = 1.

[0029] Y 3represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of heteroatoms and halogen atoms, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or -O - (M 3 E+ ) e , M 3 E+ represents a proton, a metal cation or an onium cation, E represents the valence of the cation. e represents a number such that E×e = 1.]

[0030]

[0031] [In general formula (5), R 10 and R 11 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has a heteroatom and / or a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms or an aryloxy group having 6 to 10 carbon atoms or -O - (M 5 G+ ) g , M 5 G+ represents a proton, a metal cation or an onium cation, G represents the valence of the cation. g represents a number such that G×g = 1. R 10 and R 11 optionally bond to each other to form a cyclic structure.] [2]

[0033] The electrolyte for a non-aqueous sodium ion battery according to [1], wherein the content x of the aforementioned (I) is 0.008 mass% ≤ x ≤ 7.5 mass% with respect to the total amount of the electrolyte for a non-aqueous sodium ion battery. [3]

[0035] The electrolyte for a non-aqueous sodium ion battery according to [1] or [2], wherein the counter cation of the aforementioned (I) is a lithium ion, a sodium ion, a potassium ion, a tetraalkylammonium ion, a tetraalkylphosphonium ion or an ammonium ion having a spiro ring skeleton. [4]

[0037] The electrolyte for a non-aqueous sodium ion battery according to any one of [1] to [3], wherein the content y of the aforementioned (II) is 0.08% by mass ≤ y ≤ 5.5% by mass with respect to the total amount of the electrolyte for a non-aqueous sodium ion battery. [5]

[0039] The electrolyte for a non-aqueous sodium ion battery according to any one of [1] to [4], wherein the compound having at least two isocyanate groups is at least one selected from the group consisting of pentamethylene diisocyanate and hexamethylene diisocyanate. [6]

[0041] The electrolyte for a non-aqueous sodium ion battery according to any one of [1] to [5], wherein the compound represented by the general formula (1) is selected from CH 2 (SO 2 F) 2 、CH 2 (SO 2 F)(SO 2 ONa)、CH 2 (SO 2 F)(SO 2 OCH 3 )、C(CH 3 ) 2 (SO 2 F) 2 、C(F) 2 (SO 2 F) 2 、CH 2 CH 2 (SO 2 F) 2 、CF 2 CF 2 (SO 2 F) 2 、CH 2 CH 2 (SO 2 F)(SO 2 OLi)、CH 2 CH 2 (SO 2 F)(SO 2 OCH 2 CCH)、CH 2 (SO 2 CF 3 ) 2 、CH 2 (SO 2 CF 3 )(SO 2 ONa)、and CH 2 (SO2 CF 3 )(SO 2 OCH 3 ) or at least one member of the group consisting of them. [7]

[0043] The non-aqueous sodium-ion battery electrolyte according to any one of [1] to [6], wherein the compound represented by the general formula (1) is selected from the group consisting of CH 2 (SO 2 F) 2 、CH 2 (SO 2 F)(SO 2 ONa)、CH 2 CH 2 (SO 2 F) 2 、CH 2 (SO 2 CF 3 ) 2 、and CH 2 (SO 2 CF 3 )(SO 2 ONa) or at least one member of the group consisting of them. [8]

[0045] The non-aqueous sodium-ion battery electrolyte according to any one of [1] to [7], wherein the compound represented by the general formula (2) is selected from the group consisting of CH 3 SO 2 F、C 2 H 5 SO 2 F、CH 2 =CH-SO 2 F、CF 3 CH 2 CH 2 SO 2 F、cyclohexanesulfonyl fluoride (C 6 H 11 SO 2 F)、benzenesulfonyl fluoride (C 6 H 5 SO 2 F)、CH 3 OSO 2 F、CH 3 CH 2 OSO 2 F、CH 2 =CH-OSO 2 F、CF 3 CH 2 OSO 2F, (CH 3 ) 2 CH-OSO 2 F, (CF 3 ) 2 CH-OSO 2 F, CH 3 CH 2 SO 2 CF 3 , CH 2 =CH-SO 2 CF 3 , CF 3 CH 2 CH 2 SO 2 CF 3 , CH 3 OSO 2 CF 3 , CH 3 CH 2 OSO 2 CF 3 , NaO-SO 2 CH 3 , and at least one selected from the group consisting of NaO-SO 2 CF 3 . [9]

[0047] The non-aqueous sodium ion battery electrolyte according to any one of [1] to [8], wherein the compound represented by the general formula (2) is selected from the group consisting of CH 3 SO 2 F, C 2 H 5 SO 2 F, CH 2 =CH-SO 2 F, CH 3 OSO 2 F, CH 2 =CH-OSO 2 F, CH 3 OSO 2 CF 3 , NaO-SO 2 CH 3 , and at least one selected from the group consisting of NaO-SO 2 CF 3 .

[10]

[0049] The electrolyte for a non-aqueous sodium ion battery according to any one of [1] to [9], wherein the compound represented by the general formula (5) is at least one selected from the group consisting of methanesulfonic anhydride, 1,2,5-oxadithiolane-2,2,5,5-tetraoxide, and 1,3,2,4-dioxadithiane-2,2,4,4-tetraoxide.

[11]

[0051] The electrolyte for a non-aqueous sodium ion battery according to any one of [1] to

[10] , wherein at least one selected from the group consisting of a cyclic ester, a chain ester, a cyclic ether, and a chain ether is included as the non-aqueous solvent.

[12]

[0053] The electrolyte for a non-aqueous sodium ion battery according to any one of [1] to

[11] , wherein the sodium salt is selected from NaPF 6 , NaBF 4 , NaBF 2 (C 2 O 4 ), NaPF 4 (C 2 O 4 ), NaPF 2 (C 2 O 4 ), 2 , NaSbF 6 , NaAsF 6 , NaClO 4 , NaN(SO 2 F) 2 , NaN(SO 2 CF 3 ), 2 , NaN(SO 2 F)(SO 2 CF 3 ), NaN(C a F 2a+1 SO 2 )(C b F 2b+1 SO 2 )(where a and b are integers satisfying 2 ≤ a ≤ 20 and 2 ≤ b ≤ 20.), NaSO 3 CF 3 , NaSO 3 C 4 F 9 , NaN(POF 2 ), 2 , NaN(POF 2 )(SO 2 F), NaPO 2 F2 , NaC(SO 2 CF 3 ) 3 , NaPF 3 (C 3 F 7 ) 3 , NaB(CF 3 ) 4 , NaBF 3 (C 2 F 5 ), NaAlO 2 , NaAlCl 4 , at least one selected from the group consisting of NaCl and NaI.

[13]

[0055] The non-aqueous sodium ion battery electrolyte according to any one of [1] to

[12] , wherein the concentration z of the foregoing (III) is 0.3 mol / L ≤ z ≤ 5.0 mol / L with respect to the total amount of the non-aqueous sodium ion battery electrolyte.

[14]

[0057] The non-aqueous sodium ion battery electrolyte according to any one of [1] to

[13] , further comprising at least one compound selected from the group consisting of the compound represented by the following general formula (3) and the compound represented by the following general formula (4).

[0058]

[0059] [In general formula (3), p represents an integer from 1 to 4.

[0060] R 4 and R 5 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the foregoing hydrocarbon group optionally having at least one selected from the group consisting of a heteroatom and a halogen atom, and optionally having a branched or cyclic structure when the carbon number is 3 or more), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms.

[0061] X 3 represents a phosphorus atom or a sulfur atom. When X 3 is a phosphorus atom, c = 1 and d = 1, and when X 3 is a sulfur atom, c = 2 and d = 0.

[0062] Y 4 ~Y 7Each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or -O - (M 4 F+ ) f , M 4 F+ represents a proton, a metal cation or an onium cation, F represents the valence of the cation. f represents a number such that F × f = 1.]

[0063]

[0064] [In general formula (4), R 6 ~R 9 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms.]

[15]

[0066] A non-aqueous sodium ion battery, which at least includes: a positive electrode, a negative electrode, and an electrolyte for a non-aqueous sodium ion battery according to any one of [1] to

[14] .

[16]

[0068] A method for manufacturing a non-aqueous sodium ion battery, which includes the following steps:

[0069] A step of preparing an electrolyte for a non-aqueous sodium ion battery according to any one of [1] to

[14] ;

[0070] A step of filling the aforementioned electrolyte for a non-aqueous sodium ion battery into an empty battery cell including at least a positive electrode and a negative electrode.

[0071] Effects of the Invention

[0072] According to an embodiment of the present disclosure, there is provided: an electrolyte for a non-aqueous sodium ion battery, a non-aqueous sodium ion battery using the same, and a method for manufacturing a non-aqueous sodium ion battery, which can improve at least one of the cycle characteristics at a temperature of 60 °C or higher, the gas generation amount (inhibiting effect) in a high-temperature cycle test, and the high-temperature storage characteristics of the non-aqueous sodium ion battery. Description of the Drawings

[0073] Figure 1 A graph showing the evaluation results of the discharge capacity retention rate after high-temperature cycling of Example 1-1, Comparative Examples 1-0, 1-1 to 1-2.

[0074] Figure 2 A graph showing the evaluation results of the gas generation amount during high-temperature cycling of Example 1-1, Comparative Examples 1-0, 1-1 to 1-2.

[0075] Figure 3 A graph showing the evaluation results of the restored discharge capacity retention rate after high-temperature storage of Example 1-1, Comparative Examples 1-0, 1-1 to 1-2. Detailed Description of the Invention

[0076] Hereinafter, each embodiment of the present disclosure will be described. However, the present disclosure can be implemented in various ways without departing from its gist, and is not limited to the description of the embodiments and examples exemplified below. In addition, other effects different from those brought about by the following embodiments and examples are of course understood to be brought about by the present disclosure as long as they are clearly known from the description of this specification or can be easily predicted by those skilled in the art.

[0077] In this specification, "~" is used to mean including the values described before and after it as the lower limit value and the upper limit value.

[0078] [1. Electrolyte for non-aqueous sodium ion battery]

[0079] The electrolyte for a non-aqueous sodium ion battery according to one embodiment of the present disclosure includes:

[0080] (I) Fluorosulfate (hereinafter, sometimes referred to as "Component (I)", sometimes simply referred to as "(I)");

[0081] (II) At least one selected from the group consisting of a compound having at least two isocyanate groups, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (5) (hereinafter, sometimes referred to as "Component (II)", sometimes simply referred to as "(II)");

[0082] (III) Sodium salt (hereinafter, sometimes referred to as "Component (III)", sometimes simply referred to as "(III)"); and,

[0083] (IV) Non-aqueous solvent (hereinafter, sometimes referred to as "Component (IV)", sometimes simply referred to as "(IV)").

[0084]

[0085] In general formula (1), n represents an integer of 1 to 4.

[0086] R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms.

[0087] Y 1 and Y 2 each independently represent a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or -O - (M 1 A+ ) a where M 1 A+ represents a proton, a metal cation or an onium cation, A represents the valence of the cation, and a represents a number such that A×a = 1.

[0088]

[0089] In general formula (2), R 3 represents a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or -O - (M 2 B+ ) b where M 2 B+ represents a proton, a metal cation or an onium cation, B represents the valence of the cation, and b represents a number such that B×b = 1.

[0090] Y 3represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 3 E+ ) e , M 3 E+ represents a proton, a metal cation or an onium cation, E represents the valence of the cation. e represents a number such that E×e = 1.]

[0091]

[0092] [In the general formula (5), R 10 and R 11 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has a heteroatom and / or a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, or -O - (M 5 G+ ) g , M 5 G+ represents a proton, a metal cation or an onium cation, G represents the valence of the cation. g represents a number such that G×g = 1. R 10 and R 11 optionally bond to each other to form a cyclic structure.]

[0093] In addition, if necessary, other commonly known additives can also be used in combination.

[0094] By forming the above configuration, the electrolyte for a non-aqueous sodium ion battery according to this embodiment can improve at least one of the cycle characteristics at a high temperature of 60°C or higher, the amount of gas generation (inhibiting effect) in the high-temperature cycle test, and the high-temperature storage characteristics. The details of this mechanism are not clear, but it is speculated that since component (II) is contained simultaneously with the fluorosulfate, a good coating film can be formed on the electrode.

[0095] Hereinafter, each constituent element of the electrolyte for a non-aqueous sodium ion battery according to this embodiment will be described in detail.

[0096] [(I) Fluorosulfate]

[0097] Fluorosulfate is an ionic salt having an anion and a counter cation as shown below. 3 F - The counter cation of the fluorosulfate is not particularly limited as long as it does not impair the performance of the non-aqueous sodium ion battery electrolyte and the non-aqueous sodium ion battery of the present embodiment, and various substances can be selected.

[0098] As specific examples of the counter cation, metal cations such as lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, magnesium ion, calcium ion, barium ion, silver ion, copper ion, iron ion, tetraalkylammonium ion, tetraalkylphosphonium ion, imidazolium ion, and ammonium ions having a spiro skeleton can be mentioned. Particularly, from the viewpoint of playing a role in assisting ion conduction in the non-aqueous sodium ion battery, lithium ion, sodium ion, potassium ion, tetraalkylammonium ion, tetraalkylphosphonium ion, or ammonium ion having a spiro skeleton is preferred, and lithium ion, sodium ion, tetraalkylammonium ion, or ammonium ion having a spiro skeleton is more preferred.

[0099] The number of carbon atoms of the alkyl group in the tetraalkylammonium ion is preferably 1 to 6, and the number of carbon atoms of the alkyl group in the tetraalkylphosphonium ion is preferably 1 to 6.

[0100] The four alkyl groups in the tetraalkylammonium ion may be the same or different from each other, and the four alkyl groups in the tetraalkylphosphonium ion may be the same or different from each other.

[0101] The four alkyl groups in the tetraalkylammonium ion may be the same or different from each other, and the four alkyl groups in the tetraalkylphosphonium ion may be the same or different from each other.

[0102] The ammonium ion having a spiro skeleton is preferably 5-azoniaspiroundecane, for example.

[0103] As the fluorosulfate, there is no particular limitation, and NaSO 3 F, LiSO 3 F, TEMASO 3 F, SBPSO 3 F or TEASO 3 F is particularly preferably NaSO 3 F, LiSO 3 F or TEASO 3 F. Here, TEA represents tetraethylammonium, TEMA represents triethylmethylammonium, and SBP represents 5-azoniaspiroundecane.

[0104] The content x of the fluorosulfate is not particularly limited. Relative to the total amount of the electrolyte for the non-aqueous sodium-ion battery, it is preferably 0.001% by mass or more, more preferably 0.008% by mass or more, still more preferably 0.08% by mass or more, and further preferably 1.5% by mass or more. In addition, the content of the fluorosulfate is not particularly limited. Relative to the total amount of the electrolyte for the non-aqueous sodium-ion battery, it is preferably 11.5% by mass or less, more preferably 10.5% by mass or less, still more preferably 7.5% by mass or less, and particularly preferably 5.5% by mass or less. If it is 0.001% by mass or more, at least one of the cycle characteristics at a high temperature of 60 °C or higher, the amount of gas generation (inhibiting effect) in the high-temperature cycle test, and the high-temperature storage characteristics of the non-aqueous sodium-ion battery can be improved. In addition, if it is 11.5% by mass or less, the coating film formed on the electrode will not become excessively thick, and it is not likely to cause an increase in resistance.

[0105] The fluorosulfate may be used alone or in combination of two or more in any combination and ratio according to the use.

[0106] As one mode, the content x of the aforementioned fluorosulfate is preferably 0.008% by mass ≤ x ≤ 11.5% by mass, more preferably 0.008% by mass ≤ x ≤ 10.5% by mass, still more preferably 0.008% by mass ≤ x ≤ 7.5% by mass, and particularly preferably 1.5% by mass ≤ x ≤ 5.5% relative to the total amount of the electrolyte for the non-aqueous sodium-ion battery.

[0107] [(II) is selected from at least one of the group consisting of a compound having at least two isocyanate groups, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (5)]

[0108] Hereinafter, the component (II) will be described.

[0109] The compound having at least two isocyanate groups (hereinafter, also referred to as compound A) is not particularly limited as long as it is a compound having at least two isocyanate groups.

[0110] The number of isocyanate groups in the above compound is not particularly limited as long as it is at least two, and is preferably 6 or less.

[0111] The number of isocyanate groups in the above compound is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 to 3.

[0112] The isocyanate group may be present at the end of the compound or may not be present at the end of the compound. As a preferred mode, a compound having two isocyanate groups at the end of the compound is preferred.

[0113] Compound A is not particularly limited as long as it is a compound having at least two isocyanate groups. For example, compounds having 2 to 20 carbon atoms excluding the carbon atoms of the isocyanate groups can be cited.

[0114] As a preferred embodiment, the aforementioned carbon number of compound A is preferably 2 to 12, more preferably 2 to 10, and further preferably 3 to 8.

[0115] As compounds having at least two isocyanate groups, specifically, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione, etc. can be cited.

[0116] As compounds having at least two isocyanate groups, pentamethylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, or 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione is preferred.

[0117] For the compounds represented by the general formula (1), the compounds represented by the general formula (2), and the compounds represented by the general formula (5), they are shown below.

[0118]

[0119] [In the general formula (1), n represents an integer of 1 to 4.

[0120] R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of heteroatoms and halogen atoms, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms.

[0121] Y 1 and Y 2Each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 1 A+ ) a , M 1 A+ represents a proton, a metal cation or an onium cation, A represents the valence of the cation. a represents a number such that A × a = 1.]

[0122]

[0123] [In general formula (2), R 3 represents a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 2 B+ ) b , M 2 B+ represents a proton, a metal cation or an onium cation, B represents the valence of the cation. b represents a number such that B × b = 1.

[0124] Y 3 represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 3 E+ ) e , M 3 E+ represents a proton, a metal cation or an onium cation, E represents the valence of the cation. e represents a number such that E × e = 1.]

[0125]

[0126] [In general formula (5), R 10 and R 11 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has a heteroatom and / or a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 5 G+ ) g , M 5 G+ represents a proton, a metal cation, or an onium cation, G represents the valence of the cation. g represents a number such that G×g = 1. R 10 and R 11 optionally bond to each other to form a cyclic structure.]

[0127] In this specification, a hydrocarbon group means a group having a CH structure in which a carbon atom is bonded to a hydrogen atom.

[0128] In general formula (1), n represents an integer of 1 to 4.

[0129] R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms.

[0130] As the halogen atom when R 1 and R 2 represent a halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be mentioned.

[0131] As the hydrocarbon group when R 1 and R 2 represent a hydrocarbon group having 1 to 10 carbon atoms, there is no particular limitation, and for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a group having 1 to 10 carbon atoms formed by combining these groups can be mentioned.

[0132] As R 1 and R 2 When the alkyl group is an alkyl group having 1 to 10 carbon atoms, examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, and a n-decyl group.

[0133] As R 1 and R 2 When the alkenyl group is an alkenyl group having 2 to 10 carbon atoms, examples thereof include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, and a 1,3-butadienyl group.

[0134] As R 1 and R 2 When the alkynyl group is an alkynyl group having 2 to 10 carbon atoms, examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, and a 1,1-dimethyl-2-propynyl group.

[0135] As R 1 and R 2 When the cycloalkyl group is a cycloalkyl group having 3 to 10 carbon atoms, examples thereof include a cyclopentyl group and a cyclohexyl group.

[0136] As R 1 and R 2 When the cycloalkenyl group is a cycloalkenyl group having 3 to 10 carbon atoms, examples thereof include a cyclopentenyl group and a cyclohexenyl group.

[0137] As R 1 and R 2 When the aryl group is an aryl group having 6 to 10 carbon atoms, examples thereof include a phenyl group and a naphthyl group.

[0138] The above hydrocarbon group optionally has a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0139] Any hydrogen atom of the above hydrocarbon group is optionally substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

[0140] As the hydrocarbon group having 1 to 10 carbon atoms having a halogen atom, there is no particular limitation. For example, when the number of carbon atoms is 1, examples thereof include a trifluoromethyl group.

[0141] The number of carbon atoms of the hydrocarbon group having 1 to 10 carbon atoms represents the number of carbon atoms as R 1 , R 2 .

[0142] As R 1 and R 2 When representing an alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms is not particularly limited and may be linear or branched.

[0143] As a linear alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. An alkoxy group having 1 to 3 carbon atoms is more preferred.

[0144] As a branched alkoxy group, an alkoxy group having 3 to 10 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

[0145] As R 1 and R 2 When representing an alkenyloxy group having 2 to 10 carbon atoms, the alkenyloxy group having 2 to 10 carbon atoms is not particularly limited, and may be linear or branched. An alkenyloxy group having 2 to 6 carbon atoms is preferred, and an alkenyloxy group having 2 to 3 carbon atoms is more preferred.

[0146] As R 1 and R 2 When representing an alkynyloxy group having 2 to 10 carbon atoms, the alkynyloxy group having 2 to 10 carbon atoms is not particularly limited, and may be linear or branched. An alkynyloxy group having 2 to 6 carbon atoms is preferred, and an alkynyloxy group having 2 to 3 carbon atoms is more preferred.

[0147] As R 1 and R 2 When representing a cycloalkyloxy group having 3 to 10 carbon atoms, the cycloalkyloxy group having 3 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic. A cycloalkyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkyloxy group having 3 to 6 carbon atoms is more preferred.

[0148] As R 1 and R 2 When representing a cycloalkenyloxy group having 3 to 10 carbon atoms, the cycloalkenyloxy group having 3 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic. A cycloalkenyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkenyloxy group having 3 to 6 carbon atoms is more preferred.

[0149] As R 1 and R 2 When representing an aryloxy group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic. Examples thereof include a phenoxy group and a naphthyloxy group.

[0150] When n represents an integer of 2 to 4, a plurality of R 1 may be the same or different.

[0151] When n represents an integer of 2 to 4, a plurality of R 2 may be the same or different.

[0152] As a preferred embodiment, R 1 preferably represents a hydrogen atom, a fluorine atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0153] As a preferred embodiment, R2 Preferably represents a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0154] Y 1 and Y 2 each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of heteroatoms and halogen atoms, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 1 A+ ) a where M 1 A+ represents a proton, a metal cation, or an onium cation, A represents the valence of the cation, and a represents a number such that A×a = 1.

[0155] As Y 1 and Y 2 When representing a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0156] As Y 1 and Y 2 When representing a hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group is not particularly limited. For example, it can include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a group having 1 to 10 carbon atoms formed by combining these groups.

[0157] As Y 1 and Y 2 When being an alkyl group having 1 to 10 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, a n-decyl group, etc.

[0158] As Y 1 and Y 2 When being an alkenyl group having 2 to 10 carbon atoms, examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, and a 1,3-butadienyl group, etc.

[0159] As Y 1 and Y 2 When being an alkynyl group having 2 to 10 carbon atoms, examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, and a 1,1-dimethyl-2-propynyl group, etc.

[0160] As Y1 and Y 2 When Y is a cycloalkyl group having 3 to 10 carbon atoms, examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and the like.

[0161] As Y 1 and Y 2 When Y is a cycloalkenyl group having 3 to 10 carbon atoms, examples of the cycloalkenyl group include a cyclopentenyl group, a cyclohexenyl group, and the like.

[0162] As Y 1 and Y 2 When Y is an aryl group having 6 to 10 carbon atoms, examples of the aryl group include a phenyl group, a naphthyl group, and the like.

[0163] The above hydrocarbon group optionally has a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0164] Any hydrogen atom of the above hydrocarbon group is optionally substituted by a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred.

[0165] As the hydrocarbon group having 1 to 10 carbon atoms with a halogen atom, there is no particular limitation. For example, when the carbon number is 1, examples include a trifluoromethyl group, and the like.

[0166] The carbon number of the hydrocarbon group having 1 to 10 carbon atoms represents the carbon number as Y 1 and Y 2 of the carbon number.

[0167] As Y 1 and Y 2 When Y represents an alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms is not particularly limited and may be linear or branched.

[0168] As the linear alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. More preferably, an alkoxy group having 1 to 3 carbon atoms.

[0169] As the branched alkoxy group, an alkoxy group having 3 to 10 carbon atoms is preferred, and more preferably an alkoxy group having 3 to 6 carbon atoms.

[0170] As Y 1 and Y 2 When Y represents an alkenyloxy group having 2 to 10 carbon atoms, the alkenyloxy group having 2 to 10 carbon atoms is not particularly limited and may be linear or branched. An alkenyloxy group having 2 to 6 carbon atoms is preferred, and more preferably an alkenyloxy group having 2 to 3 carbon atoms.

[0171] As Y 1 and Y 2When it represents an alkynyloxy group having 2 to 10 carbon atoms, the alkynyloxy group having 2 to 10 carbon atoms is not particularly limited and may be linear or branched, preferably an alkynyloxy group having 2 to 6 carbon atoms, more preferably an alkynyloxy group having 2 to 3 carbon atoms.

[0172] As Y 1 and Y 2 When it represents a cycloalkyloxy group having 3 to 10 carbon atoms, the cycloalkyloxy group having 3 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic, preferably a cycloalkyloxy group having 3 to 8 carbon atoms, more preferably a cycloalkyloxy group having 3 to 6 carbon atoms.

[0173] As Y 1 and Y 2 When it represents a cycloalkenyloxy group having 3 to 10 carbon atoms, the cycloalkenyloxy group having 3 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic, preferably a cycloalkenyloxy group having 3 to 8 carbon atoms, more preferably a cycloalkenyloxy group having 3 to 6 carbon atoms.

[0174] As Y 1 and Y 2 When it represents an aryloxy group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic, and examples thereof include a phenoxy group and a naphthyloxy group.

[0175] M 1 A+ M represents a proton, a metal cation or an onium cation, and A represents the valence of the cation.

[0176] As M 1 A+ When M represents a metal cation, examples of the metal cation include alkali metal cations such as a lithium ion, a sodium ion and a potassium ion, and alkaline earth metal cations such as a magnesium ion and a calcium ion.

[0177] As M 1 A+ When M represents an onium cation, examples of the onium cation include a trialkylammonium ion, a tetraalkylammonium ion, a tetraalkylphosphonium ion, an imidazolium ion, and an ammonium ion having a spiro ring skeleton.

[0178] A represents the valence of the cation. M 1 A+ When M represents a monovalent cation, A is 1, and M 1 A+ When M represents a divalent cation, A is 2.

[0179] M 1 A+ Preferably, M represents a metal cation, more preferably a lithium ion or a sodium ion, and particularly preferably a sodium ion.

[0180] As a preferred embodiment, Y 1 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -O - (M 1 A+ ) a .

[0181] As a preferred embodiment, Y 2 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -O - (M 1 A+ ) a .

[0182] Specific examples of the compound represented by the general formula (1) are shown below, but the present disclosure is not limited to these.

[0183]

[0184] In the general formula (2), R 3 represents a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 2 B+ ) b , M 2 B+ represents a proton, a metal cation or an onium cation, B represents the valence of the cation. b represents a number such that B × b = 1.

[0185] As the hydrocarbon group when R 3 represents a hydrocarbon group having 1 to 10 carbon atoms, there is no particular limitation, and for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a group having 1 to 10 carbon atoms formed by combining these groups can be mentioned.

[0186] As the alkyl group when R 3 is an alkyl group having 1 to 10 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, etc. can be mentioned.

[0187] As R 3When the alkenyl group has 2 to 10 carbon atoms, examples of the alkenyl group include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl.

[0188] As R 3 When the alkynyl group has 2 to 10 carbon atoms, examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl.

[0189] As R 3 When the cycloalkyl group has 3 to 10 carbon atoms, examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and the like.

[0190] As R 3 When the cycloalkenyl group has 3 to 10 carbon atoms, examples of the cycloalkenyl group include cyclopentenyl, cyclohexenyl, and the like.

[0191] As R 3 When the aryl group has 6 to 10 carbon atoms, examples of the aryl group include phenyl, naphthyl, and the like.

[0192] The above hydrocarbon groups optionally have a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0193] Any hydrogen atom of the above hydrocarbon group is optionally substituted by a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred.

[0194] The hydrocarbon group having 1 to 10 carbon atoms with a halogen atom is not particularly limited. For example, when the carbon number is 1, examples include trifluoromethyl and the like.

[0195] The carbon number of the hydrocarbon group having 1 to 10 carbon atoms represents the carbon number as R 3 of.

[0196] As R 3 The hydrocarbon group having 1 to 10 carbon atoms as R may or may not be methyl. That the hydrocarbon group having 1 to 10 carbon atoms as R is not methyl means excluding "methyl" itself from the hydrocarbon group having 1 to 10 carbon atoms as R 3 of. 3 The hydrocarbon group having 1 to 10 carbon atoms as R excludes "methyl" itself.

[0197] As R 3 When representing an alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms is not particularly limited and may be linear or branched.

[0198] As the linear alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. An alkoxy group having 1 to 3 carbon atoms is more preferred.

[0199] As the branched alkoxy group, an alkoxy group having 3 to 10 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

[0200] The alkoxy group having 1 to 10 carbon atoms may optionally have a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred.

[0201] As R 3 When representing an alkenyloxy group having 2 to 10 carbon atoms, the alkenyloxy group having 2 to 10 carbon atoms is not particularly limited, and may be linear or branched, and an alkenyloxy group having 2 to 6 carbon atoms is preferred, and an alkenyloxy group having 2 to 3 carbon atoms is more preferred.

[0202] As R 3 When representing an alkynyloxy group having 2 to 10 carbon atoms, the alkynyloxy group having 2 to 10 carbon atoms is not particularly limited, and may be linear or branched, and an alkynyloxy group having 2 to 6 carbon atoms is preferred, and an alkynyloxy group having 2 to 3 carbon atoms is more preferred.

[0203] As R 3 When representing a cycloalkyloxy group having 3 to 10 carbon atoms, the cycloalkyloxy group having 3 to 10 carbon atoms is not particularly limited, and may be a monocyclic or polycyclic, and a cycloalkyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkyloxy group having 3 to 6 carbon atoms is more preferred.

[0204] As R 3 When representing a cycloalkenyloxy group having 3 to 10 carbon atoms, the cycloalkenyloxy group having 3 to 10 carbon atoms is not particularly limited, and may be a monocyclic or polycyclic, and a cycloalkenyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkenyloxy group having 3 to 6 carbon atoms is more preferred.

[0205] As R 3 When representing an aryloxy group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms is not particularly limited, and may be a monocyclic or polycyclic, and examples thereof include a phenoxy group and a naphthyloxy group.

[0206] M 2 B+ Represents a proton, a metal cation or an onium cation, and B represents the valence of the cation.

[0207] As M 2 B+ When representing a metal cation, examples of the metal cation include alkali metal cations such as a lithium ion, a sodium ion, a potassium ion, etc., and alkaline earth metal cations such as a magnesium ion, a calcium ion, etc.

[0208] As M 2 B+ When representing an onium cation, examples of the onium cation include a trialkylammonium ion, a tetraalkylammonium ion, a tetraalkylphosphonium ion, an imidazolium ion, an ammonium ion having a spiro ring skeleton, etc.

[0209] B represents the valence of the cation. M 2B+ When representing a monovalent cation, B is 1, and M 2 B+ When representing a divalent cation, B is 2.

[0210] M 2 B+ Preferably represents a metal cation, more preferably a lithium ion or a sodium ion, and particularly preferably a sodium ion.

[0211] As a preferred embodiment, R 3 Preferably represents a hydrocarbon group having 1 to 10 carbon atoms other than a methyl group, an alkoxy group having 1 to 10 carbon atoms, or -O - (M 2 B+ ) b .

[0212] Y 3 Represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when having 3 or more carbon atoms, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 3 E+ ) e , M 3 E+ Represents a proton, a metal cation or an onium cation, E represents the valence of the cation. e represents a number such that E×e = 1.

[0213] As Y 3 When representing a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0214] As Y 3 When representing a hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a group having 1 to 10 carbon atoms formed by combining these groups.

[0215] As Y 3 When being an alkyl group having 1 to 10 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, a n-decyl group, etc.

[0216] As Y 3When the alkenyl group has 2 to 10 carbon atoms, examples of the alkenyl group include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl.

[0217] As Y 3 When the alkynyl group has 2 to 10 carbon atoms, examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl.

[0218] As Y 3 When the cycloalkyl group has 3 to 10 carbon atoms, examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and the like.

[0219] As Y 3 When the cycloalkenyl group has 3 to 10 carbon atoms, examples of the cycloalkenyl group include cyclopentenyl, cyclohexenyl, and the like.

[0220] As Y 3 When the aryl group has 6 to 10 carbon atoms, examples of the aryl group include phenyl, naphthyl, and the like.

[0221] The above hydrocarbon groups optionally have a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0222] Any hydrogen atom of the above hydrocarbon group is optionally substituted by a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred.

[0223] As the hydrocarbon group having 1 to 10 carbon atoms with a halogen atom, there is no particular limitation. For example, when the carbon number is 1, trifluoromethyl and the like can be mentioned.

[0224] The carbon number of the hydrocarbon group having 1 to 10 carbon atoms represents the carbon number as Y 3 of.

[0225] As Y 3 When representing an alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms is not particularly limited and may be linear or branched.

[0226] As the linear alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. An alkoxy group having 1 to 3 carbon atoms is more preferred.

[0227] As the branched alkoxy group, an alkoxy group having 3 to 10 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

[0228] The alkoxy group having 1 to 10 carbon atoms optionally has a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred.

[0229] As Y 3When it represents an alkenyloxy group having 2 to 10 carbon atoms, the alkenyloxy group having 2 to 10 carbon atoms is not particularly limited and may be linear or branched, preferably an alkenyloxy group having 2 to 6 carbon atoms, more preferably an alkenyloxy group having 2 to 3 carbon atoms.

[0230] As Y 3 When it represents an alkynyloxy group having 2 to 10 carbon atoms, the alkynyloxy group having 2 to 10 carbon atoms is not particularly limited and may be linear or branched, preferably an alkynyloxy group having 2 to 6 carbon atoms, more preferably an alkynyloxy group having 2 to 3 carbon atoms.

[0231] As Y 3 When it represents a cycloalkyloxy group having 3 to 10 carbon atoms, the cycloalkyloxy group having 3 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic, preferably a cycloalkyloxy group having 3 to 8 carbon atoms, more preferably a cycloalkyloxy group having 3 to 6 carbon atoms.

[0232] As Y 3 When it represents a cycloalkenyloxy group having 3 to 10 carbon atoms, the cycloalkenyloxy group having 3 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic, preferably a cycloalkenyloxy group having 3 to 8 carbon atoms, more preferably a cycloalkenyloxy group having 3 to 6 carbon atoms.

[0233] As Y 3 When it represents an aryloxy group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic, and examples thereof include a phenoxy group and a naphthyloxy group.

[0234] M 3 E+ M represents a proton, a metal cation or an onium cation, and E represents the valence of the cation.

[0235] As M 3 E+ When M represents a metal cation, examples of the metal cation include alkali metal cations such as a lithium ion, a sodium ion and a potassium ion, and alkaline earth metal cations such as a magnesium ion and a calcium ion.

[0236] As M 3 E+ When M represents an onium cation, examples of the onium cation include a trialkylammonium ion, a tetraalkylammonium ion, a tetraalkylphosphonium ion, an imidazolium ion, and an ammonium ion having a spiro ring skeleton.

[0237] E represents the valence of the cation. M 3 E+ When M represents a monovalent cation, E is 1, and M 3 E+ When M represents a divalent cation, E is 2.

[0238] M 3E+ Preferably represents a metal cation, more preferably a lithium ion or a sodium ion, and particularly preferably a sodium ion.

[0239] As a preferred embodiment, Y 3 Preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms other than a methyl group, an alkoxy group having 1 to 10 carbon atoms, or -O - (M 3 E+ ) e .

[0240] Specific examples of the compound represented by the general formula (2) are shown below, but the present disclosure is not limited to these.

[0241]

[0242] In the general formula (5), R 10 and R 11 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has a heteroatom and / or a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 5 G+ ) g , M 5 G+ represents a proton, a metal cation or an onium cation, G represents the valence of the cation. g represents a number such that G×g = 1. R 10 and R 11 optionally bond to each other to form a cyclic structure.

[0243] As the halogen atom when R 10 and R 11 represent a halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0244] As the hydrocarbon group when R 10 and R 11 represent a hydrocarbon group having 1 to 10 carbon atoms, there is no particular limitation, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a group having 1 to 10 carbon atoms formed by combining these groups.

[0245] As R 10 and R 11When the alkyl group is an alkyl group having 1 to 10 carbon atoms, examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group, and a n-decyl group.

[0246] As R 10 and R 11 When the alkenyl group is an alkenyl group having 2 to 10 carbon atoms, examples thereof include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, and a 1,3-butadienyl group.

[0247] As R 10 and R 11 When the alkynyl group is an alkynyl group having 2 to 10 carbon atoms, examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, and a 1,1-dimethyl-2-propynyl group.

[0248] As R 10 and R 11 When the cycloalkyl group is a cycloalkyl group having 3 to 10 carbon atoms, examples thereof include a cyclopentyl group and a cyclohexyl group.

[0249] As R 10 and R 11 When the cycloalkenyl group is a cycloalkenyl group having 3 to 10 carbon atoms, examples thereof include a cyclopentenyl group and a cyclohexenyl group.

[0250] As R 10 and R 11 When the aryl group is an aryl group having 6 to 10 carbon atoms, examples thereof include a phenyl group and a naphthyl group.

[0251] The above hydrocarbon groups optionally have a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, and a boron atom.

[0252] Any hydrogen atom of the above hydrocarbon groups is optionally substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

[0253] As the hydrocarbon group having 1 to 10 carbon atoms having a halogen atom, there is no particular limitation. For example, when the carbon number is 1, examples thereof include a trifluoromethyl group.

[0254] The carbon number of the hydrocarbon group having 1 to 10 carbon atoms represents the carbon number as R 10 and R 11 of.

[0255] As R 10 and R 11 When representing an alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms is not particularly limited and may be linear or branched.

[0256] As a linear alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. An alkoxy group having 1 to 3 carbon atoms is more preferred.

[0257] As a branched alkoxy group, an alkoxy group having 3 to 10 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

[0258] The alkoxy group having 1 to 10 carbon atoms may optionally have a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred.

[0259] As R 10 and R 11 When representing an alkenyloxy group having 2 to 10 carbon atoms, the alkenyloxy group having 2 to 10 carbon atoms is not particularly limited, and may be linear or branched. An alkenyloxy group having 2 to 6 carbon atoms is preferred, and an alkenyloxy group having 2 to 3 carbon atoms is more preferred.

[0260] As R 10 and R 11 When representing an alkynyloxy group having 2 to 10 carbon atoms, the alkynyloxy group having 2 to 10 carbon atoms is not particularly limited, and may be linear or branched. An alkynyloxy group having 2 to 6 carbon atoms is preferred, and an alkynyloxy group having 2 to 3 carbon atoms is more preferred.

[0261] As R 10 and R 11 When representing a cycloalkyloxy group having 3 to 10 carbon atoms, the cycloalkyloxy group having 3 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic. A cycloalkyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkyloxy group having 3 to 6 carbon atoms is more preferred.

[0262] As R 10 and R 11 When representing a cycloalkenyloxy group having 3 to 10 carbon atoms, the cycloalkenyloxy group having 3 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic. A cycloalkenyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkenyloxy group having 3 to 6 carbon atoms is more preferred.

[0263] As R 10 and R 11 When representing an aryloxy group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic, and examples include a phenoxy group, a naphthyloxy group, etc.

[0264] M 5 G+ represents a proton, a metal cation or an onium cation, and G represents the valence of the cation.

[0265] As M 5 G+When representing a metal cation, examples of the metal cation include alkali metal cations such as lithium ion, sodium ion, and potassium ion, and alkaline earth metal cations such as magnesium ion and calcium ion.

[0266] As M 5 G+ When representing an onium cation, examples of the onium cation include trialkylammonium ion, tetraalkylammonium ion, tetraalkylphosphonium ion, imidazolium ion, and ammonium ion having a spiro ring skeleton.

[0267] G represents the valence of the cation. M 5 G+ When representing a monovalent cation, G is 1, and M 5 G+ When representing a divalent cation, G is 2.

[0268] M 5 G+ Preferably represents a metal cation, more preferably lithium ion or sodium ion, and particularly preferably sodium ion.

[0269] As a preferred embodiment, R 10 and R 11 Preferably represent a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0270] As another preferred embodiment, R 10 and R 11 Preferably bond to each other to form a cyclic structure. Among them, it preferably forms a cyclic structure of a five-membered ring or a six-membered ring together with -S-O-S- in the general formula (5).

[0271] Specific examples of the compound represented by the general formula (5) are shown below, but the present disclosure is not limited to these.

[0272]

[0273] The aforementioned compound having at least 2 isocyanate groups is preferably at least one selected from the group consisting of pentamethylene diisocyanate and hexamethylene diisocyanate.

[0274] The aforementioned compound represented by the general formula (1) is preferably selected from the group consisting of CH 2 (SO 2 F) 2 , CH 2 (SO 2 F)(SO 2 ONa), CH 2 (SO 2 F)(SO 2 OCH 3 ), C(CH 3 )2 (SO 2 F) 2 、C(F) 2 (SO 2 F) 2 , CH 2 CH 2 (SO 2 F) 2 CF 2 CF 2 (SO 2 F) 2 , CH 2 CH 2 (SO 2 F)(SO 2 OLi), CH 2 CH 2 (SO 2 F)(SO 2 OCH 2 CCH), CH 2 (SO 2 CF 3 ) 2 , CH 2 (SO 2 CF 3 )(SO 2 ONa), and CH 2 (SO 2 CF 3 )(SO 2 OCH 3 ) is selected from the group consisting of:

[0275] It should be noted that the above compounds correspond to the compounds described as specific examples of the compound represented by the above general formula (1).

[0276] Among them, the compound represented by the above general formula (1) is preferably selected from CH 2 (SO 2 F) 2 , CH 2 (SO 2 F)(SO 2 ONa)、CH 2 CH 2 (SO 2 F) 2 , CH 2 (SO 2 CF 3 ) 2 , and CH 2 (SO 2 CF 3 )(SO 2At least one selected from the group consisting of ONa).

[0277] The compound represented by the general formula (2) is preferably selected from the group consisting of CH 3 SO 2 F, C 2 H 5 SO 2 F, CH 2 =CH-SO 2 F, CF 3 CH 2 CH 2 SO 2 F, cyclohexanesulfonyl fluoride (C 6 H 11 SO 2 F), benzenesulfonyl fluoride (C 6 H 5 SO 2 F), CH 3 OSO 2 F, CH 3 CH 2 OSO 2 F, CH 2 =CH-OSO 2 F, CF 3 CH 2 OSO 2 (CH 3 ) 2 CH-OSO 2 (CF 3 ) 2 CH-OSO 2 F, CH 3 CH 2 SO 2 CF 3 , CH 2 =CH-SO 2 CF 3 , CF 3 CH 2 CH 2 SO 2 CF 3 , CH 3 OSO 2 CF 3 , CH 3 CH 2 OSO 2 CF 3 , NaO-SO 2 CH 3 , and at least one selected from the group consisting of NaO-SO 2 CF 3 .

[0278] It should be noted that the above-mentioned compounds respectively correspond to the compounds described as specific examples of the compounds represented by the above general formula (2).

[0279] Among them, the compound represented by the aforementioned general formula (2) is preferably selected from the group consisting of CH 3 SO 2 F, C 2 H 5 SO 2 F, CH 2 =CH-SO 2 F, CH 3 OSO 2 F, CH 2 =CH-OSO 2 F, CH 3 OSO 2 CF 3 , NaO-SO 2 CH 3 , and NaO-SO 2 CF 3 and at least one selected from the group consisting of.

[0280] As one mode, the compound represented by the aforementioned general formula (2) is preferably selected from the group consisting of C 2 H 5 SO 2 F, CH 2 =CH-SO 2 F, CF 3 CH 2 CH 2 SO 2 F, cyclohexanesulfonyl fluoride (C 6 H 11 SO 2 F), benzenesulfonyl fluoride (C 6 H 5 SO 2 F), CH 3 OSO 2 F, CH 3 CH 2 OSO 2 F, CH 2 =CH-OSO 2 F, CF 3 CH 2 OSO 2 F, (CH 3 ) 2 CH-OSO 2 F, (CF 3 ) 2 CH-OSO 2 F, CH 3 CH2 SO 2 CF 3 , CH 2 =CH-SO 2 CF 3 CF 3 CH 2 CH 2 SO 2 CF 3 , CH 3 OSO 2 CF 3 , CH 3 CH 2 OSO 2 CF 3 、NaO-SO 2 CH 3 , and NaO-SO 2 CF 3 At least one of the group consisting of.

[0281] In one embodiment, the compound represented by the general formula (2) is preferably selected from the group consisting of C 2 H 5 SO 2 F, CH 2 =CH-SO 2 F, CH 3 OSO 2 F, CH 2 =CH-OSO 2 F, CH 3 OSO 2 CF 3 、NaO-SO 2 CH 3 , and NaO-SO 2 CF 3 At least one of the group consisting of.

[0282] The compound represented by the general formula (5) is preferably at least one selected from the group consisting of methanesulfonic anhydride, 1,2,5-oxadithiolane-2,2,5,5-tetraoxide and 1,3,2,4-dioxadithiane-2,2,4,4-tetraoxide.

[0283] The content y of component (II) is not particularly limited. Relative to the total amount of the non-aqueous sodium-ion battery electrolyte, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, further preferably 0.08% by mass or more, particularly preferably 0.1% by mass or more, and most preferably 0.8% by mass or more. In addition, the content y of component (II) is not particularly limited. Relative to the total amount of the non-aqueous sodium-ion battery electrolyte, it is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, further preferably 5.5% by mass or less, still more preferably 5.0% by mass or less, particularly preferably 3.5% by mass or less, and most preferably 2.5% by mass or less. If it is 0.01% by mass or more, at least one of the cycle characteristics at a high temperature of 60 °C or higher, the gas generation amount (inhibiting effect) in the high-temperature cycle test, and the high-temperature storage characteristics of the non-aqueous sodium-ion battery can be improved. In addition, if it is 10.0% by mass or less, the coating film formed on the electrode will not become excessively thick, and it is not likely to cause an increase in resistance.

[0284] Component (II) can be used alone or in combination of two or more in any combination and ratio according to the use.

[0285] As one mode, the content y of component (II) relative to the total amount of the non-aqueous sodium-ion battery electrolyte is preferably 0.01% by mass ≤ y ≤ 10.0% by mass, more preferably 0.03% by mass ≤ y ≤ 8.0% by mass, further preferably 0.08% by mass ≤ y ≤ 5.5% by mass, still more preferably 0.1% by mass ≤ y ≤ 5.0% by mass, particularly preferably 0.1% by mass ≤ y ≤ 3.5% by mass, and most preferably 0.8% by mass ≤ y ≤ 2.5% by mass.

[0286] [(III) Sodium salt]

[0287] The type of the sodium salt of the solute is not particularly limited, and any sodium salt (excluding the aforementioned fluorosulfate) can be used. As a specific example, it can be cited as selected from NaPF 6 , NaBF 4 , NaBF 2 (C 2 O 4 ), NaPF 4 (C 2 O 4 ), NaPF 2 (C 2 O 4 ) 2 , NaSbF 6 , NaAsF 6 , NaClO 4 , NaN(SO 2 F) 2 , NaN(SO 2 CF3 ) 2 , NaN(SO 2 F)(SO 2 CF 3 ), NaN(C a F 2a+1 SO 2 )(C b F 2b+1 SO 2 )(Here, a and b are integers satisfying 2 ≤ a ≤ 20 and 2 ≤ b ≤ 20.)、NaSO 3 CF 3 、NaSO 3 C 4 F 9 、NaN(POF 2 ) 2 、NaN(POF 2 )(SO 2 F)、NaPO 2 F 2 、NaC(SO 2 CF 3 ) 3 、NaPF 3 (C 3 F 7 ) 3 、NaB(CF 3 ) 4 、NaBF 3 (C 2 F 5 )、NaAlO 2 、NaAlCl 4 、At least one electrolyte sodium salt represented by at least one of the group consisting of NaCl and NaI. These solutes can be used alone or two or more can be mixed in any combination and ratio according to the use. Among them, considering the energy density, power characteristics, life, etc. of the battery, NaPF 6 、NaBF 2 (C 2 O 4 )、NaPF 4 (C 2 O 4 )、NaPF 2 (C 2 O 4 ) 2 、NaN(SO 2 F) 2 、NaN(SO 2 CF 3 ) 2 、NaN(SO 2 C2 F 5 ) 2 、NaN(POF 2 ) 2 、NaN(POF 2 )(SO 2 F)、NaPO 2 F 2 , more preferably NaPF 6 、NaN(SO 2 F) 2 , further preferably NaPF 6 .

[0288] The non-aqueous sodium-ion battery electrolyte described above may include NaPF 6 as a preferred embodiment of the aforementioned (III) sodium salt.

[0289] There is no particular limitation on the concentration z of the sodium salt in the non-aqueous sodium-ion battery electrolyte of the present embodiment. Relative to the total amount of the non-aqueous sodium-ion battery electrolyte, it is preferably 0.05 mol / L or more, more preferably 0.3 mol / L or more, further preferably 0.8 mol / L or more. Additionally, it is preferably 5.0 mol / L or less, more preferably 2.0 mol / L or less, further preferably 1.5 mol / L or less.

[0290] By setting it to 0.05 mol / L or more, it becomes easier to suppress the deterioration of the cycle characteristics of the non-aqueous sodium-ion battery caused by the decrease in ionic conductivity. On the other hand, by setting it to 5.0 mol / L or less, it becomes easier to suppress the increase in the viscosity of the non-aqueous sodium-ion battery electrolyte and the deterioration of the battery characteristics caused by the accompanying decrease in ionic conductivity.

[0291] Component (III) can be used alone or in any combination and ratio of two or more according to the application.

[0292] As one embodiment, the concentration z of component (III) relative to the total amount of the non-aqueous sodium-ion battery electrolyte is preferably 0.3 mol / L ≤ z ≤ 5.0 mol / L, more preferably 0.4 mol / L ≤ z ≤ 3.0 mol / L, further preferably 0.5 mol / L ≤ z ≤ 2.0 mol / L, and particularly preferably 0.8 mol / L ≤ z ≤ 1.5 mol / L.

[0293] The above-mentioned sodium salt (III) has substances that are the same as the above-mentioned component (II). If the content is above the specified amount (the concentration of the sodium salt (III) in the non-aqueous sodium-ion battery electrolyte is 0.3 mol / L or more relative to the total amount of the non-aqueous sodium-ion battery electrolyte), it acts as the main electrolyte (sodium salt (III)). If it is below the specified amount, it acts as an additive (component (II)).

[0294] It should be noted that the above-mentioned component (II) is a compound different from the above-mentioned sodium salt (III).

[0295] For example, when the sodium salt (III) is CF 3 SO 3 Na, the above-mentioned component (II) is a compound other than CF 3 SO 3 Na.

[0296] [(IV) Non-aqueous solvent]

[0297] The type of non-aqueous solvent is not particularly limited, and any non-aqueous solvent can be used. As specific examples, the following non-aqueous solvents can be cited.

[0298] As cyclic esters, in addition to cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate, γ-butyrolactone, γ-valerolactone, etc. can also be cited.

[0299] As linear esters, in addition to linear carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, etc. can also be cited.

[0300] As cyclic ethers, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, etc. can be cited.

[0301] As linear ethers, dimethoxyethane, diethoxyethane, diethyl ether, ethoxymethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, etc. can be cited.

[0302] As sulfur-containing non-aqueous solvents, dimethyl sulfoxide, sulfolane, etc. can be cited.

[0303] In addition, the non-aqueous solvent used in this embodiment can be used alone, or two or more can be mixed in any combination and ratio according to the use.

[0304] As a preferred embodiment, the non-aqueous sodium-ion battery electrolyte can include at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, and linear ethers as the above-mentioned non-aqueous solvent.

[0305] As a preferred embodiment, the non-aqueous electrolyte for a sodium-ion battery may include a cyclic ester as the non-aqueous solvent, and the cyclic ester is preferably a cyclic carbonate. Additionally, as another preferred embodiment, the non-aqueous electrolyte for a sodium-ion battery may include a linear ester as the non-aqueous solvent, and the linear ester is preferably a linear carbonate.

[0306] Furthermore, the non-aqueous electrolyte for a sodium-ion battery more preferably contains at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, methyl acetate, ethyl acetate, ethyl propionate, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxyethane, diethoxyethane, ethoxymethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether as the non-aqueous solvent.

[0307] These non-aqueous solvents can be used individually or in combination of two or more in any ratio according to the application.

[0308] [Other Additives]

[0309] Other additives commonly used in non-aqueous electrolytes for sodium-ion batteries can be added to the non-aqueous electrolyte of this embodiment in any ratio as long as the gist of the present disclosure is not deviated from.

[0310] As a preferred embodiment, the non-aqueous electrolyte for a sodium-ion battery of this embodiment preferably further contains at least one compound selected from the group consisting of the compound represented by the following general formula (3) and the compound represented by the following general formula (4).

[0311]

[0312] [In general formula (3), p represents an integer from 1 to 4.

[0313] R 4 and R 5 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the number of carbon atoms is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.

[0314] X 3 represents a phosphorus atom or a sulfur atom. X3 When X is a phosphorus atom, c = 1 and d = 1. 3 When X is a sulfur atom, c = 2 and d = 0.

[0315] Y 4 ~Y 7 each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 4 F+ ) f where M 4 F+ represents a proton, a metal cation or an onium cation, F represents the valence of the cation, and f represents a number such that F×f = 1.]

[0316]

[0317] [In general formula (4), R 6 ~R 9 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the carbon number is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.]

[0318] As the halogen atom when R 4 and R 5 represent a halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be mentioned.

[0319] As the hydrocarbon group when R 4 and R 5 represent a hydrocarbon group having 1 to 10 carbon atoms, there is no particular limitation, and for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a group having 1 to 10 carbon atoms formed by combining these groups can be mentioned.

[0320] As R 4 and R 5When the alkyl group is an alkyl group having 1 to 10 carbon atoms, examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and the like.

[0321] As R 4 and R 5 When the alkenyl group is an alkenyl group having 2 to 10 carbon atoms, examples include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl.

[0322] As R 4 and R 5 When the alkynyl group is an alkynyl group having 2 to 10 carbon atoms, examples include ethynyl, 1-propynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl.

[0323] As R 4 and R 5 When the cycloalkyl group is a cycloalkyl group having 3 to 10 carbon atoms, examples include cyclopentyl, cyclohexyl, and the like.

[0324] As R 4 and R 5 When the cycloalkenyl group is a cycloalkenyl group having 3 to 10 carbon atoms, examples include cyclopentenyl, cyclohexenyl, and the like.

[0325] As R 4 and R 5 When the aryl group is an aryl group having 6 to 10 carbon atoms, examples include phenyl, naphthyl, and the like.

[0326] The above hydrocarbon groups optionally have a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0327] Any hydrogen atom of the above hydrocarbon groups is optionally substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred.

[0328] As the hydrocarbon group having 1 to 10 carbon atoms having a halogen atom, there is no particular limitation. For example, when the carbon number is 1, examples include trifluoromethyl and the like.

[0329] The carbon number of the hydrocarbon group having 1 to 10 carbon atoms represents the carbon number as R 4 , R 5 .

[0330] As R 4 and R 5 When representing an alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms has no particular limitation and may be linear or branched.

[0331] As a linear alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. An alkoxy group having 1 to 3 carbon atoms is more preferred.

[0332] As a branched alkoxy group, an alkoxy group having 3 to 10 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

[0333] As R 4 and R 5 When representing an alkenyloxy group having 2 to 10 carbon atoms, the alkenyloxy group having 2 to 10 carbon atoms is not particularly limited, and may be linear or branched. An alkenyloxy group having 2 to 6 carbon atoms is preferred, and an alkenyloxy group having 2 to 3 carbon atoms is more preferred.

[0334] As R 4 and R 5 When representing an alkynyloxy group having 2 to 10 carbon atoms, the alkynyloxy group having 2 to 10 carbon atoms is not particularly limited, and may be linear or branched. An alkynyloxy group having 2 to 6 carbon atoms is preferred, and an alkynyloxy group having 2 to 3 carbon atoms is more preferred.

[0335] As R 4 and R 5 When representing a cycloalkyloxy group having 3 to 10 carbon atoms, the cycloalkyloxy group having 3 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic. A cycloalkyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkyloxy group having 3 to 6 carbon atoms is more preferred.

[0336] As R 4 and R 5 When representing a cycloalkenyloxy group having 3 to 10 carbon atoms, the cycloalkenyloxy group having 3 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic. A cycloalkenyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkenyloxy group having 3 to 6 carbon atoms is more preferred.

[0337] As R 4 and R 5 When representing an aryloxy group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms is not particularly limited, and may be monocyclic or polycyclic. Examples thereof include a phenoxy group and a naphthyloxy group.

[0338] As a preferred embodiment, R 4 preferably represents a hydrogen atom, a fluorine atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0339] As a preferred embodiment, R 5 preferably represents a hydrogen atom, a fluorine atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0340] As Y 4 to Y 7 When representing a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

[0341] As Y 4 ~Y 7 When representing a hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group is not particularly limited. For example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a group having 1 to 10 carbon atoms formed by combining these groups can be cited.

[0342] As Y 4 ~Y 7 When the alkyl group has 1 to 10 carbon atoms, examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and the like.

[0343] As Y 4 ~Y 7 When the alkenyl group has 2 to 10 carbon atoms, examples of the alkenyl group include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, and 1,3-butadienyl.

[0344] As Y 4 ~Y 7 When the alkynyl group has 2 to 10 carbon atoms, examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, and 1,1-dimethyl-2-propynyl.

[0345] As Y 4 ~Y 7 When the cycloalkyl group has 3 to 10 carbon atoms, examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and the like.

[0346] As Y 4 ~Y 7 When the cycloalkenyl group has 3 to 10 carbon atoms, examples of the cycloalkenyl group include cyclopentenyl, cyclohexenyl, and the like.

[0347] As Y 4 ~Y 7 When the aryl group has 6 to 10 carbon atoms, examples of the aryl group include phenyl, naphthyl, and the like.

[0348] The above hydrocarbon group optionally has a heteroatom. Examples of the heteroatom include an oxygen atom, a sulfur atom, a nitrogen atom, and the like.

[0349] Any hydrogen atom of the above hydrocarbon group is optionally substituted by a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred.

[0350] As the hydrocarbon group having 1 to 10 carbon atoms having a halogen atom, it is not particularly limited. For example, when the carbon number is 1, trifluoromethyl and the like can be cited.

[0351] The number of carbon atoms of a hydrocarbon group having 1 to 10 carbon atoms is represented as Y 4 ~Y 7 represents the number of carbon atoms.

[0352] As Y 4 ~Y 7 When representing an alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms is not particularly limited and may be linear or branched.

[0353] As a linear alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. An alkoxy group having 1 to 3 carbon atoms is more preferred.

[0354] As a branched alkoxy group, an alkoxy group having 3 to 10 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

[0355] As Y 4 ~Y 7 When representing an alkenyloxy group having 2 to 10 carbon atoms, the alkenyloxy group having 2 to 10 carbon atoms is not particularly limited and may be linear or branched. An alkenyloxy group having 2 to 6 carbon atoms is preferred, and an alkenyloxy group having 2 to 3 carbon atoms is more preferred.

[0356] As Y 4 ~Y 7 When representing an alkynyloxy group having 2 to 10 carbon atoms, the alkynyloxy group having 2 to 10 carbon atoms is not particularly limited and may be linear or branched. An alkynyloxy group having 2 to 6 carbon atoms is preferred, and an alkynyloxy group having 2 to 3 carbon atoms is more preferred.

[0357] As Y 4 ~Y 7 When representing a cycloalkoxy group having 3 to 10 carbon atoms, the cycloalkoxy group having 3 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic. A cycloalkoxy group having 3 to 8 carbon atoms is preferred, and a cycloalkoxy group having 3 to 6 carbon atoms is more preferred.

[0358] As Y 4 ~Y 7 When representing a cycloalkenyloxy group having 3 to 10 carbon atoms, the cycloalkenyloxy group having 3 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic. A cycloalkenyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkenyloxy group having 3 to 6 carbon atoms is more preferred.

[0359] As Y 4 ~Y 7 When representing an aryloxy group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic. Examples include phenoxy group and naphthyloxy group.

[0360] M 4 F+represents a proton, a metal cation or an onium cation, and F represents the valence of the cation.

[0361] As M 4 F+ When M represents a metal cation, examples of the metal cation include alkali metal cations such as lithium ion, sodium ion, potassium ion, and alkaline earth metal cations such as magnesium ion, calcium ion.

[0362] As M 4 F+ When M represents an onium cation, examples of the onium cation include trialkylammonium ion, tetraalkylammonium ion, tetraalkylphosphonium ion, imidazolium ion, ammonium ion having a spiro ring skeleton, etc.

[0363] F represents the valence of the cation. M 4 F+ When M represents a monovalent cation, F is 1, and M 4 F+ When M represents a divalent cation, F is 2.

[0364] M 4 F+ Preferably, M represents a metal cation, more preferably lithium ion or sodium ion, and particularly preferably sodium ion.

[0365] As a preferred embodiment, Y 4 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -O - (M 4 F+ ) f .

[0366] As a preferred embodiment, Y 5 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -O - (M 4 F+ ) f .

[0367] As a preferred embodiment, Y 6 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -O - (M 4 F+ ) f .

[0368] As a preferred embodiment, Y 7 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or -O - (M 4 F+ )f 。

[0369] Specific examples of the compound represented by the general formula (3) are shown below, but the present disclosure is not limited to these.

[0370]

[0371] In the general formula (4), R 6 ~R 9 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms (the aforementioned hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the number of carbon atoms is 3 or more, optionally has a branched or cyclic structure), an alkoxy group having 1 to 10 carbon atoms (the aforementioned alkoxy group optionally has a halogen atom), an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.

[0372] As the halogen atom when R 6 ~R 9 represents a halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be mentioned.

[0373] As the hydrocarbon group when R 6 ~R 9 represents a hydrocarbon group having 1 to 10 carbon atoms, there is no particular limitation, and for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a group having 1 to 10 carbon atoms formed by combining these groups can be mentioned.

[0374] As the alkyl group when R 6 ~R 9 is an alkyl group having 1 to 10 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, etc. can be mentioned.

[0375] As the alkenyl group when R 6 ~R 9 is an alkenyl group having 2 to 10 carbon atoms, vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, etc. can be mentioned.

[0376] As the alkynyl group when R 6 ~R 9 is an alkynyl group having 2 to 10 carbon atoms, ethynyl, 1-propynyl, 2-propynyl, 1,1-dimethyl-2-propynyl, etc. can be mentioned.

[0377] As R 6 ~R9 When the cycloalkyl group is a cycloalkyl group having 3 to 10 carbon atoms, cyclopentyl, cyclohexyl, etc. can be mentioned.

[0378] As R 6 ~R 9 When the cycloalkenyl group is a cycloalkenyl group having 3 to 10 carbon atoms, cyclopentenyl, cyclohexenyl, etc. can be mentioned.

[0379] As R 6 ~R 9 When the aryl group is an aryl group having 6 to 10 carbon atoms, phenyl, naphthyl, etc. can be mentioned.

[0380] The above hydrocarbon group optionally has a heteroatom. As the heteroatom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. can be mentioned.

[0381] Any hydrogen atom of the above hydrocarbon group is optionally substituted by a halogen atom. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred.

[0382] As the hydrocarbon group having 1 to 10 carbon atoms having a halogen atom, there is no particular limitation. For example, when the carbon number is 1, trifluoromethyl, etc. can be mentioned.

[0383] The carbon number of the hydrocarbon group having 1 to 10 carbon atoms represents the carbon number as R 6 ~R 9 of the carbon number.

[0384] As R 6 ~R 9 When representing an alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms is not particularly limited and can be linear or branched.

[0385] As the linear alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred. An alkoxy group having 1 to 3 carbon atoms is more preferred.

[0386] As the branched alkoxy group, an alkoxy group having 3 to 10 carbon atoms is preferred, and an alkoxy group having 3 to 6 carbon atoms is more preferred.

[0387] The alkoxy group having 1 to 10 carbon atoms optionally has a halogen atom. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferred.

[0388] As R 6 ~R 9 When representing an alkenyloxy group having 2 to 10 carbon atoms, the alkenyloxy group having 2 to 10 carbon atoms is not particularly limited and can be linear or branched. An alkenyloxy group having 2 to 6 carbon atoms is preferred, and an alkenyloxy group having 2 to 3 carbon atoms is more preferred.

[0389] As R 6 ~R9 When the alkynyloxy group has 2 to 10 carbon atoms, the alkynyloxy group having 2 to 10 carbon atoms is not particularly limited and may be linear or branched. An alkynyloxy group having 2 to 6 carbon atoms is preferred, and an alkynyloxy group having 2 to 3 carbon atoms is more preferred.

[0390] As R 6 ~R 9 When the cycloalkyloxy group has 3 to 10 carbon atoms, the cycloalkyloxy group having 3 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic. A cycloalkyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkyloxy group having 3 to 6 carbon atoms is more preferred.

[0391] As R 6 ~R 9 When the cycloalkenyloxy group has 3 to 10 carbon atoms, the cycloalkenyloxy group having 3 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic. A cycloalkenyloxy group having 3 to 8 carbon atoms is preferred, and a cycloalkenyloxy group having 3 to 6 carbon atoms is more preferred.

[0392] As R 6 ~R 9 When the aryloxy group has 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms is not particularly limited and may be monocyclic or polycyclic. Examples thereof include a phenoxy group and a naphthyloxy group.

[0393] As a preferred embodiment, R 6 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. As the hydrocarbon group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms is preferred.

[0394] As a preferred embodiment, R 7 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. As the hydrocarbon group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms is preferred.

[0395] As a preferred embodiment, R 8 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. As the hydrocarbon group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms is preferred.

[0396] As a preferred embodiment, R 9 preferably represents a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. As the hydrocarbon group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms is preferred.

[0397] Specific examples of the compound represented by the general formula (4) are shown below, but the present disclosure is not limited to these.

[0398]

[0399]

[0400] In addition, as "other additives" other than the above, cyclohexylbenzene, biphenyl, tert-butylbenzene, tert-amylbenzene, fluorobenzene, vinylene carbonate, oligomers of vinylene carbonate (number average molecular weight is 170 to 5000. Here, the number average molecular weight refers to the number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the solvent. The same applies hereinafter.), ethylene carbonate, difluoroanisole, fluoroethylene carbonate, ethylene acetylenedicarboxylate, trans-difluoroethylene carbonate, dimethylvinylene carbonate, 1 , 3,2-dioxazolothiophene-2,2-dioxide, 4-propyl-1,3,2-dioxazolothiophene-2,2-dioxide, methyl methanedisulfonate, succinonitrile, (ethoxy) pentafluorocyclotriphosphazene, tetrafluoro(pyridinecarboxylic acid) phosphate, and 1,3-dimethyl-1,3-divinyl-1,3-bis(1,1,1,3,3,3-hexafluoroisopropyl) disiloxane and other compounds having an overcharge prevention effect, a negative electrode film formation effect, and a positive electrode protection effect.

[0401] Regarding the content of fluoroethylene carbonate in the non-aqueous sodium ion battery electrolyte of the present embodiment, from the viewpoint of gas generation, it is preferably not excessive, and fluoroethylene carbonate may be substantially absent. Substantially absent means "less than 0.001% by mass relative to the total amount of the above electrolyte".

[0402] As a preferred mode, a mode in which the non-aqueous sodium ion battery electrolyte of the present embodiment does not contain fluoroethylene carbonate can be cited.

[0403] Regarding the content of 1,3,2-dioxazolothiophene-2,2-dioxide and / or 4-propyl-1,3,2-dioxazolothiophene-2,2-dioxide in the non-aqueous sodium ion battery electrolyte of the present embodiment, from the viewpoint of storage stability, it is preferably not excessive. Regarding the content of 1,3,2-dioxazolothiophene-2,2-dioxide and / or 4-propyl-1,3,2-dioxazolothiophene-2,2-dioxide, from the viewpoint of storage stability, it is preferably not excessive, and it may also be substantially absent.

[0404] As a preferred embodiment, a non-aqueous sodium-ion battery electrolyte according to this embodiment may be exemplified by one that does not contain 1,3,2-dioxazolothiophene-2,2-dioxide and / or 4-propyl-1,3,2-dioxazolothiophene-2,2-dioxide.

[0405] When the non-aqueous sodium-ion battery electrolyte according to this embodiment further contains at least one compound selected from the group consisting of the compounds represented by the above general formula (3) and the compounds represented by the above general formula (4), the content of at least one compound selected from the group consisting of the compounds represented by the above general formula (3) and the compounds represented by the above general formula (4) is preferably 0.01% by mass or more and 10% by mass or less based on the total amount of the electrolyte.

[0406] When the non-aqueous sodium-ion battery electrolyte according to this embodiment contains the above other additives, the content is preferably 0.01% by mass or more and 10% by mass or less based on the total amount of the electrolyte.

[0407] In addition, the above sodium salts (sodium salts other than the sodium salts used as solutes (excluding those equivalent to the aforementioned component (I) and the aforementioned component (II))) can also be used as other additives.

[0408] When the above sodium salts are used as other additives, the content of the other additives is preferably 0.3% by mass or more and 1.5% by mass or less based on the total amount of the electrolyte.

[0409] In addition, the other additives can also be a gelling agent or a crosslinked polymer. The non-aqueous sodium-ion battery electrolyte according to this embodiment can be quasi-solidified using a gelling agent or a crosslinked polymer, and the quasi-solidified product is suitable for, for example, sodium polymer batteries.

[0410] [2. Non-aqueous sodium-ion battery]

[0411] Next, the configuration of a non-aqueous sodium-ion battery according to one embodiment of the present disclosure will be described.

[0412] The aforementioned non-aqueous sodium-ion battery includes at least: a positive electrode, a negative electrode, and the non-aqueous sodium-ion battery electrolyte according to this embodiment.

[0413] The non-aqueous sodium-ion battery according to this embodiment is characterized in that the non-aqueous sodium-ion battery electrolyte according to this embodiment is used, and components used in a general non-aqueous sodium-ion battery are used in other constituent members. That is, other constituent members include: a positive electrode and a negative electrode capable of absorbing and releasing sodium, a current collector, a separator, a housing, etc.

[0414] [Positive electrode]

[0415] As the positive electrode material (positive electrode active material), there is no particular limitation. For example, NaCrO is used.2 , NaFe 0.5 Co 0.5 O 2 , NaFe 0.4 Mn 0.3 Ni 0.3 O 2 , NaNi 0.5 Ti 0.3 Mn 0.2 O 2 , Na 2 / 3 Ni 1 / 3 Ti 1 / 6 Mn 1 / 2 O 2 , Na 2 / 3 Ni 1 / 3 Mn 2 / 3 O 2 etc., sodium-containing transition metal composite oxides, those formed by mixing multiple transition metals such as Co, Mn, Ni, etc. in these sodium-containing transition metal composite oxides, those in which a part of the transition metals in these sodium-containing transition metal composite oxides are replaced by other metals other than transition metals, NaFePO 4 , NaVPO 4 F, Na 3 V 2 (PO 4 ) 3 , Na 2 Fe 2 (SO 4 ) 3 etc., polyanion-type compounds, TiO 2 , V 2 O 5 , MoO 3 etc., oxides, TiS 2 , FeS, etc., sulfides, or conductive polymers such as polyacetylene, polyphenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, carbon materials, etc.

[0416] In the positive electrode, for example, a positive electrode active material layer is formed on at least one surface of the positive electrode current collector. The positive electrode active material layer is composed of, for example, the aforementioned positive electrode active material, a binder, and, if necessary, a conductive agent. Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, or styrene-butadiene rubber (SBR) resin. As the conductive agent, for example, carbon materials such as acetylene black, Ketjen black, carbon fiber, or graphite (granular graphite, flake graphite) can be used, and acetylene black or Ketjen black with low crystallinity is preferably used.

[0417] [Negative electrode]

[0418] As the negative electrode material (negative electrode active material), there is no particular limitation, and examples thereof include sodium metal or a material capable of absorbing and releasing sodium ions. For example, sodium metal, an alloy of sodium metal and other metals such as tin, an intermetallic compound, various carbon materials typified by hard carbon, metal oxides such as titanium oxide, metal nitrides, tin (elemental), tin compounds, activated carbon, conductive polymers, etc. In addition to these, phosphorus (elemental) such as red phosphorus and black phosphorus, phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, Mo-P, antimony (elemental), antimony compounds such as Sb / C and Bi-Sb, etc. can also be used. These negative electrode active materials can be used alone or in combination of two or more.

[0419] In the negative electrode, for example, a negative electrode active material layer is formed on at least one surface of the negative electrode current collector. The negative electrode active material layer is composed of, for example, the aforementioned negative electrode active material, a binder, and a conductive agent as needed. As the binder, examples include polytetrafluoroethylene, polyvinylidene fluoride, or styrene-butadiene rubber (SBR) resin. As the conductive agent, for example, carbon materials such as acetylene black, Ketjen black, carbon fiber, or graphite (granular graphite, flake graphite) can be used.

[0420] [Current collector]

[0421] Copper, aluminum, stainless steel, nickel, titanium, or their alloys, etc. can be used for the current collectors of the positive electrode and the negative electrode. An active material layer is formed on at least one surface of the current collector.

[0422] [Separator]

[0423] As the separator for preventing contact between the positive electrode and the negative electrode, a non-woven fabric, a porous sheet, or a film formed of polyolefin (e.g., polypropylene, polyethylene), paper, and glass fiber, etc. is used. Those that are preferably micro-porous and impregnated with an electrolytic solution so that ions can easily pass through are used.

[0424] [Outer casing]

[0425] As the outer casing, for example, a coin-type, cylindrical-type, square-type, etc. metal can, a laminated outer casing can be used. As the metal can material, for example, nickel-plated iron steel sheet, stainless steel sheet, nickel-plated stainless steel sheet, aluminum or its alloy, nickel, titanium, etc. can be cited. As the laminated outer casing, for example, an aluminum laminated film, a SUS laminated film, a laminated film of polypropylene, polyethylene, etc. coated with silica can be used.

[0426] The configuration of the non-aqueous sodium ion battery of this embodiment is not particularly limited. For example, a configuration in which a positive electrode and a negative electrode are disposed opposite to each other and a non-aqueous electrolytic solution is enclosed in an outer casing can be formed. In addition, the shape of the non-aqueous sodium ion battery of this embodiment is not particularly limited, and shapes such as coin-shaped, cylindrical, square, or aluminum laminated sheet type can be formed.

[0427] [Method for manufacturing non-aqueous sodium ion battery]

[0428] In addition, the present disclosure also relates to a method for manufacturing a non-aqueous sodium ion battery.

[0429] The aforementioned manufacturing method is a method for manufacturing a non-aqueous sodium ion battery, and includes the following steps:

[0430] A step of preparing an electrolyte for the non-aqueous sodium ion battery of the present disclosure;

[0431] A step of filling the aforementioned electrolyte for the non-aqueous sodium ion battery into an empty battery cell having at least a positive electrode and a negative electrode.

[0432] Examples

[0433] Hereinafter, the present disclosure will be specifically described based on examples, but the present disclosure is not limited to these examples.

[0434] [Preparation of electrolyte for non-aqueous sodium ion battery]

[0435] (Preparation of electrolyte No. NaSO 3 F(2.0)-PDI(1.0))

[0436] Using a mixed solvent obtained by mixing propylene carbonate (hereinafter also referred to as "PC"), ethylene carbonate (hereinafter also referred to as "EC"), and ethyl methyl carbonate (hereinafter also referred to as "EMC") in a volume ratio of PC:EC:EMC = 30:20:50 as the (IV) non-aqueous solvent, and dissolving NaPF as the (III) sodium salt 6 , sodium fluorosulfate as the (I) fluorosulfate (hereinafter also referred to as "NaSO 3 F"), and pentamethylene diisocyanate (PDI) as the (II) in the solvent so as to have the concentrations described in Table 1, to prepare electrolyte No. NaSO 3 F(2.0)-PDI(1.0). The above preparation is carried out while maintaining the liquid temperature within the range of 20 to 30 °C.

[0437] In Tables 1, 8, 10, and 12 below, the concentrations (mass %) of the (I) fluorosulfate, component (II), and other additives represent the content (mass %) relative to the total amount of the electrolyte for the non-aqueous sodium ion battery.

[0438] In Tables 1, 8, 10, and 12 below, the concentration (mol / L) of the (III) sodium salt represents the concentration relative to the total amount of the electrolyte for the non-aqueous sodium ion battery.

[0439] [Table 1]

[0440] Table 1

[0441] Electrolyte composition

[0442]

[0443] (Preparation of other electrolytes in Table 1)

[0444] In addition, change the concentration of (I), the type and concentration of (II) to those described in Table 1. Except for this, prepare various electrolytes described in Table 1 in the same way as electrolyte No. NaSO 3 F(2.0)-PDI(1.0). It should be noted that the abbreviations in the table are as described below.

[0445] PDI: Pentamethylene diisocyanate

[0446] HDI: Hexamethylene diisocyanate

[0447] MBSF: CH 2 (SO 2 F) 2

[0448] ESF: C 2 H 5 SO 2 F

[0449] MSAn: Methanesulfonic anhydride

[0450] ODTO: 1,2,5-Oxadithiolane-2,2,5,5-tetraoxide

[0451] [Examples 1-1, Comparative Examples 1-0 to 1-2]

[0452] For test batteries made using the electrolytes described in Table 2 as test electrolytes, NaNi 0.5 Ti 0.3 Mn 0.2 O 2 as the positive electrode material and hard carbon (manufactured by KUREHA CORPORATION, Carbotron P) as the negative electrode material, perform a high-temperature cycle test, and evaluate the cycle characteristics, the gas generation amount during the high-temperature cycle test, and the high-temperature storage characteristics respectively. The evaluation results are shown in Table 2. It should be noted that the test battery cells are made as follows.

[0453] The test positive electrode is made according to the following steps.

[0454] Mix 90% by mass of NaNi 0.5 Ti 0.3 Mn 0.2 O 2, 5% by mass of acetylene black as a conductive agent and 5% by mass of polyvinylidene fluoride (PVDF) as a binder are mixed, and N-methylpyrrolidone as a solvent is further added in such a way that it accounts for 50% by mass of the total mass of the aforementioned positive electrode active material, conductive agent, and binder to prepare a slurry solution. The slurry solution is coated on an aluminum foil as a positive electrode current collector and dried at 150 °C for 12 hours to obtain a test positive electrode having a positive electrode active material layer formed on the current collector.

[0455] The test negative electrode is fabricated according to the following steps.

[0456] 90% by mass of hard carbon powder (Carbotron P, manufactured by KUREHA CORPORATION) as a negative electrode active material and 10% by mass of polyvinylidene fluoride (PVDF) as a binder are mixed, and N-methylpyrrolidone as a solvent is further added in such a way that it accounts for 50% by mass of the total mass of the aforementioned negative electrode active material and binder to prepare a slurry solution. The slurry solution is coated on an aluminum foil as a negative electrode current collector and dried at 150 °C for 12 hours to obtain a test negative electrode having a negative electrode active material layer formed on the current collector.

[0457] The test positive electrode and the test negative electrode are arranged with a polyethylene separator impregnated with a test electrolyte therebetween, and a 50 mAh test battery cell with an aluminum laminated case is assembled.

[0458] [High-temperature cycle characteristics evaluation]

[0459] For the test battery, at an ambient temperature of 25 °C, the upper charge voltage is set to 4.1 V and the lower discharge voltage is set to 1.5 V, and charge and discharge are carried out by the constant current-constant voltage method at a current density of 0.32 mA / cm 2 After charge and discharge, a charge and discharge test is carried out at an ambient temperature of 60 °C to evaluate the cycle characteristics. Charging is carried out until 4.1 V and discharging is carried out until 1.5 V at a current density of 1.56 mA / cm 2 The charge and discharge cycles are repeated. Then, the deterioration of the battery cell is evaluated by the discharge capacity retention rate of the 500th cycle in the charge and discharge test at an ambient temperature of 60 °C.

[0460] The "discharge capacity retention rate after high-temperature cycling" expressed by the discharge capacity retention rate of the 500th cycle is calculated by the following formula. Note that the discharge capacity of the first cycle in the charge and discharge test at an ambient temperature of 60 °C is taken as the initial discharge capacity.

[0461] Discharge capacity retention rate after high-temperature cycling (%) = (Discharge capacity of the 500th cycle / Initial discharge capacity) × 100

[0462] [Evaluation of gas generation amount]

[0463] Before and after the implementation of the above high-temperature cycle characteristic evaluation, according to the Archimedes method using silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., silicone oil KF54), the volume of the battery cell was measured, and the gas generation amount V (unit: cm 3 )(Gas generation amount V = volume V2 of the battery cell after the implementation of the high-temperature cycle characteristic evaluation - volume V1 of the battery cell before the implementation of the high-temperature cycle characteristic evaluation). Based on this gas generation amount V, the "gas generation amount during high-temperature cycling" was evaluated.

[0464] [Evaluation of high-temperature storage characteristics]

[0465] For the test battery, at an ambient temperature of 25°C, using the constant current and constant voltage method, with a current density of 0.32 mA / cm 2 charging was carried out until the charging upper limit voltage of 4.1 V was reached, and then, with a constant current of 0.32 mA / cm 2 discharging was carried out until 1.5 V. The same charge and discharge cycle was repeated 10 times. The discharge capacity of the 10th cycle was defined as the "initial discharge capacity". After that, at an ambient temperature of 25°C, using the constant current and constant voltage method, with a current density of 0.32 mA / cm 2 charging was carried out until the charging upper limit voltage of 4.1 V was reached. It was stored at 60°C for 4 weeks, and after the battery was cooled to 25°C, at an ambient temperature of 25°C, discharging was carried out with a constant current of 0.32 mA / cm 2 until 1.5 V. Using the constant current and constant voltage method, with a current density of 0.32 mA / cm 2 charging was carried out until the charging upper limit voltage of 4.1 V, and then discharging was carried out with a constant current of 0.32 mA / cm 2 until 1.5 V. The discharge capacity at this time was defined as the "recovery capacity". The "maintenance rate of the recovery discharge capacity after high-temperature storage" was calculated using the following formula.

[0466] <Maintenance rate of the recovery discharge capacity after high-temperature storage>

[0467] Maintenance rate of the recovery discharge capacity after high-temperature storage (%) = (recovery capacity / initial discharge capacity) × 100

[0468] [Table 2]

[0469] Table 2

[0470]

[0471] The evaluation results of the examples and comparative examples in Table 2 are relative values with the evaluation result of Comparative Example 1-0 as 100%. Similarly, the same applies to Tables 3 to 7 hereafter.

[0472] It should be noted that, for the "discharge capacity retention rate after high-temperature cycling", the larger the value, the more ideal it is; for the "discharge capacity recovery retention rate after high-temperature storage", the larger the value, the more ideal it is; and for the "gas generation amount during high-temperature cycling", the smaller the value, the more ideal it is.

[0473] Judging from the evaluation results in Table 2: By making the non-aqueous electrolyte contain (I) and (II) simultaneously (Example 1-1), compared with the result of simply adding the addition effects of the case where only (I) is contained (Comparative Example 1-1) and the case where only (II) is contained (Comparative Example 1-2), the discharge capacity retention rate after high-temperature cycling is further improved ( Figure 1 ).

[0474] In addition, regarding the inhibitory effect on the gas generation amount during high-temperature cycling and the discharge capacity recovery retention rate after high-temperature storage, a further improvement tendency similar to the above was also confirmed ( Figure 2 , Figure 3 ).

[0475] The mechanism underlying the above-mentioned further improvement tendency is unclear, but it is speculated that by making the non-aqueous electrolyte contain (I) and (II) simultaneously, a good film is formed on the electrode.

[0476] [Examples 1-2 to 1-6, Comparative Examples 1-3 to 1-7]

[0477] Using the electrolytes described in Tables 3 to 7 as the test electrolytes, and in other respects, test battery cells were fabricated in the same manner as in Example 1-1, and performance evaluations were carried out. The evaluation results are shown in Tables 3 to 7.

[0478] [Table 3]

[0479] Table 3

[0480]

[0481] [Table 4]

[0482] Table 4

[0483]

[0484] [Table 5]

[0485] Table 5

[0486]

[0487] [Table 6]

[0488] Table 6

[0489]

[0490] [Table 7]

[0491] Table 7

[0492]

[0493] From the evaluation results in Tables 3 to 7, even when changing the type of (II), as in Example 1-1, a further improvement tendency was confirmed for the discharge capacity retention rate after high-temperature cycling, the inhibitory effect on the gas generation amount during high-temperature cycling, and the restored discharge capacity retention rate after high-temperature storage.

[0494] [Examples 2-1 to 2-8, Comparative Examples 2-1 to 2-10]

[0495] The composition of the electrolytic solution was changed to the electrolytic solution composition described in Table 8. Except for this, various electrolytic solutions described in Table 8 were prepared in the same manner as for Electrolyte No. NaSO 3 F(2.0)-PDI(1.0).

[0496] The electrolytic solutions described in Table 9 were used as the test electrolytic solutions. Except for this, test cells were fabricated in the same manner as in Example 1-1, and performance evaluations were performed. The evaluation results are shown in Table 9.

[0497] [Table 8]

[0498] Table 8

[0499] Electrolytic solution composition

[0500]

[0501] [Table 9]

[0502] Table 9

[0503]

[0504] From the evaluation results in Table 9, it was determined that: even when the concentration of various (I) was changed, by making the non-aqueous electrolytic solution contain (I) and (II) simultaneously, at least one of the discharge capacity retention rate after high-temperature cycling, the inhibitory effect on the gas generation amount during high-temperature cycling, and the restored discharge capacity retention rate after high-temperature storage was further improved compared to the result of simply adding the addition effects of the case of containing only the corresponding (I) (Comparative Examples 2-1 to 2-8) and the case of containing only (II) (Comparative Example 2-9).

[0505] In particular, it was found that: when the concentration of (I) was 0.1 to 7.0% by mass, the improvement effect was large.

[0506] DMC represents dimethyl carbonate.

[0507] The evaluation results of the examples and comparative examples in Table 9 use the evaluation results of Comparative Examples 2-10 as a relative value of 100%. Additionally, the same applies to all subsequent tables.

[0508] [Examples 3-1 to 3-6, Comparative Examples 3-1 to 3-6]

[0509] Change the composition of the electrolytic solution to the electrolytic solution composition described in Table 10. Except for this, prepare various electrolytic solutions described in Table 10 in the same manner as Electrolyte No. NaSO 3 F(2.0)-PDI(1.0).

[0510] Use the electrolytic solution described in Table 11 as the test electrolytic solution. Except for this, fabricate the test battery in the same manner as in Example 1-1 and conduct performance evaluation. The evaluation results are shown in Table 11.

[0511] [Table 10]

[0512] Table 10

[0513] Electrolytic solution composition

[0514]

[0515] [Table 11]

[0516] Table 11

[0517]

[0518] It is determined from the evaluation results in Table 11 that even when the concentrations of various changes (II) are different, by making the non-aqueous electrolytic solution contain (I) and (II) simultaneously, compared with the result of simply adding the addition effects of the case where only (I) is contained (Comparative Example 2-5) and the case where only the corresponding (II) is contained (Comparative Examples 3-1 to 3-6), at least one of the discharge capacity retention rate after high-temperature cycling, the inhibitory effect on gas generation during high-temperature cycling, and the recovery discharge capacity retention rate after high-temperature storage is further improved.

[0519] In particular, it is determined that when the concentration of (II) is 0.1 to 5% by mass, the improvement effect is significant.

[0520] [Examples 4-1 to 4-9, Comparative Examples 4-1 to 4-8]

[0521] Change the composition of the electrolytic solution to the electrolytic solution composition described in Table 12. Except for this, prepare various electrolytic solutions described in Table 12 in the same manner as Electrolyte No. NaSO 3 F(2.0)-PDI(1.0).

[0522] The electrolyte described in Table 13 was used as the test electrolyte. Except for this, test batteries were fabricated in the same manner as in Example 1-1, and performance evaluations were conducted. The evaluation results are shown in Table 13.

[0523] It should be noted that the abbreviations in the table are as follows.

[0524] DFPMSF: 1-(Difluorophosphinyl)methanesulfonylfluoride

[0525] MBPD: Methylenebis(phosphonic difluoride)

[0526] TVS: Tetravinylsilane

[0527] MSF: Methanesulfonyl fluoride (CH 3 SO 2 F)

[0528] [Table 12]

[0529] Table 12

[0530] Electrolyte composition

[0531]

[0532] [Table 13]

[0533] Table 13

[0534]

[0535] It was determined from the results in Table 13 that when other additives were also contained, at least one of the discharge capacity retention rate after high-temperature cycling, the suppression effect of the gas generation amount during high-temperature cycling, and the recovery discharge capacity retention rate after high-temperature storage was further improved.

[0536] Industrial applicability

[0537] According to the present disclosure, it is possible to provide: a non-aqueous sodium ion battery electrolyte that can improve at least one of the cycling characteristics at a temperature of 60°C or higher, the gas generation amount (suppression effect) during a high-temperature cycling test, and the high-temperature storage characteristics of a non-aqueous sodium ion battery, a non-aqueous sodium ion battery using the same, and a method for manufacturing a non-aqueous sodium ion battery.

[0538] The present disclosure has been described in detail with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the gist and scope of the present disclosure.

[0539] This application is based on Japanese Patent Application No. 2022-181330 filed on November 11, 2022, the content of which is incorporated herein by reference.

Claims

1. An electrolyte for a non-aqueous sodium-ion battery, comprising: (I) Fluorosulfate; (II) At least one selected from the group consisting of a compound having at least two isocyanate groups, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (5); (III) Sodium salt; and, (IV) A non-aqueous solvent, In general formula (1), n represents an integer from 1 to 4, R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. The hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom. When the hydrocarbon group has 3 or more carbon atoms, it optionally has a branched or cyclic structure. Y 1 and Y 2 each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyloxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 1 A+ ) a , M 1 A+ represents a proton, a metal cation or an onium cation, A represents the valence of the cation, a represents a number such that A×a = 1, the hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the hydrocarbon group has 3 or more carbon atoms, it optionally has a branched or cyclic structure In general formula (2), R 3 represents a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 2 B+ ) b , M 2 B+ represents a proton, a metal cation or an onium cation, B represents the valence of the cation, b represents a number such that B×b = 1, the hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the hydrocarbon group has 3 or more carbon atoms, it optionally has a branched or cyclic structure, and the alkoxy group optionally has a halogen atom. Y 3 represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 3 E+ ) e , M 3 E+ represents a proton, a metal cation or an onium cation, E represents the valence of the cation, e represents a number such that E×e = 1, the hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, when the hydrocarbon group has 3 or more carbon atoms, it optionally has a branched or cyclic structure, and the alkoxy group optionally has a halogen atom In general formula (5), R 10 and R 11 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or -O - (M 5 G+ ) g , M 5 G+ represents a proton, a metal cation or an onium cation, G represents the valence of the cation, g represents a number such that G×g = 1, R 10 and R 11 optionally bond to each other to form a cyclic structure, the hydrocarbon group optionally has a heteroatom and / or a halogen atom, and when the hydrocarbon group has 3 or more carbon atoms, it optionally has a branched or cyclic structure, and the alkoxy group optionally has a halogen atom.

2. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The content x of (I) is 0.008% by mass ≤ x ≤ 7.5% by mass relative to the total amount of the electrolyte for a non-aqueous sodium-ion battery.

3. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The counter cation of (I) is lithium ion, sodium ion, potassium ion, tetraalkylammonium ion, tetraalkylphosphonium ion or ammonium ion having a spiro ring skeleton.

4. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The content y of (II) is 0.08% by mass ≤ y ≤ 5.5% by mass relative to the total amount of the electrolyte for a non-aqueous sodium-ion battery.

5. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The compound having at least two isocyanate groups is at least one selected from the group consisting of pentamethylene diisocyanate and hexamethylene diisocyanate.

6. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The compound represented by the general formula (1) is selected from the group consisting of CH 2 (SO 2 F) 2 、CH 2 (SO 2 F)(SO 2 ONa)、CH 2 (SO 2 F)(SO 2 OCH 3 )、C(CH 3 ) 2 (SO 2 F) 2 、C(F) 2 (SO 2 F) 2 、CH 2 CH 2 (SO 2 F) 2 、CF 2 CF 2 (SO 2 F) 2 、CH 2 CH 2 (SO 2 F)(SO 2 OLi)、CH 2 CH 2 (SO 2 F)(SO 2 OCH 2 CCH)、CH 2 (SO 2 CF 3 ) 2 、CH 2 (SO 2 CF 3 )(SO 2 ONa)、and CH 2 (SO 2 CF 3 )(SO 2 OCH 3 ), and at least one selected from the group consisting of 7. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The compound represented by the general formula (1) is selected from the group consisting of CH 2 (SO 2 F) 2 、CH 2 (SO 2 F)(SO 2 ONa)、CH 2 CH 2 (SO 2 F) 2 、CH 2 (SO 2 CF 3 ) 2 、and CH 2 (SO 2 CF 3 )(SO 2 ONa), and at least one selected from the group consisting thereof.

8. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The compound represented by the general formula (2) is selected from the group consisting of CH 3 SO 2 F, C 2 H 5 SO 2 F, CH 2 =CH-SO 2 F, CF 3 CH 2 CH 2 SO 2 F, cyclohexanesulfonyl fluoride (C 6 H 11 SO 2 F), benzenesulfonyl fluoride (C 6 H 5 SO 2 F), CH 3 OSO 2 F, CH 3 CH 2 OSO 2 F, CH 2 =CH-OSO 2 F, CF 3 CH 2 OSO 2 F, (CH 3 ) 2 CH-OSO 2 F, (CF 3 ) 2 CH-OSO 2 F, CH 3 CH 2 SO 2 CF 3 , CH 2 =CH-SO 2 CF 3 , CF 3 CH 2 CH 2 SO 2 CF 3 , CH 3 OSO 2 CF 3 , CH 3 CH 2 OSO 2 CF 3 , NaO-SO 2 CH 3 , and NaO-SO 2 CF 3 and at least one selected from the group consisting of.

9. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The compound represented by the general formula (2) is selected from the group consisting of CH 3 SO 2 F, C 2 H 5 SO 2 F, CH 2 =CH-SO 2 F, CH 3 OSO 2 F, CH 2 =CH-OSO 2 F, CH 3 OSO 2 CF 3 , NaO-SO 2 CH 3 , and NaO-SO 2 CF 3 and at least one member selected from the group consisting thereof.

10. The electrolyte for a non-aqueous sodium-ion battery according to claim 1, wherein, The compound represented by the general formula (5) is at least one selected from the group consisting of methanesulfonic anhydride, 1,2,5-oxadithiolane-2,2,5,5-tetraoxide, and 1,3,2,4-dioxadithiane-2,2,4,4-tetraoxide.

11. The electrolyte for a non-aqueous sodium-ion battery according to any one of claims 1 to 10, wherein, Contains at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, and chain ethers as the non-aqueous solvent.

12. The electrolyte for a non-aqueous sodium-ion battery according to any one of claims 1 to 10, wherein, The sodium salt is selected from the group consisting of NaPF 6 , NaBF 4 , NaBF 2 (C 2 O 4 ), NaPF 4 (C 2 O 4 ), NaPF 2 (C 2 O 4 ) 2 , NaSbF 6 , NaAsF 6 , NaClO 4 , NaN(SO 2 F) 2 , NaN(SO 2 CF 3 ) 2 , NaN(SO 2 F)(SO 2 CF 3 ), NaN(C a F 2a+1 SO 2 )(C b F 2b+1 SO 2 ), NaSO 3 CF 3 , NaSO 3 C 4 F 9 , NaN(POF 2 ) 2 , NaN(POF 2 )(SO 2 F), NaPO 2 F 2 , NaC(SO 2 CF 3 ) 3 , NaPF 3 (C 3 F 7 ) 3 , NaB(CF 3 ) 4 , NaBF 3 (C 2 F 5 ), NaAlO 2 , NaAlCl 4 , NaCl, and at least one selected from the group consisting of NaI, wherein, NaN(C a F 2a+1 SO 2 )(C b F 2b+1 SO 2 wherein a and b are integers satisfying 2 ≤ a ≤ 20 and 2 ≤ b ≤ 20.

13. The electrolyte for a non-aqueous sodium-ion battery according to any one of claims 1 to 10, wherein, The concentration z of (III) is 0.3 mol / L ≤ z ≤ 5.0 mol / L relative to the total amount of the electrolyte for a non-aqueous sodium-ion battery.

14. The electrolyte for a non-aqueous sodium-ion battery according to any one of claims 1 to 10, wherein, Further contains at least one compound selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4), In general formula (3), p represents an integer from 1 to 4, R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, the hydrocarbon group optionally having at least one selected from the group consisting of a heteroatom and a halogen atom, and when the hydrocarbon group has 3 or more carbon atoms, optionally having a branched or cyclic structure X 3 represents a phosphorus atom or a sulfur atom, where X 3 when X is a phosphorus atom, c = 1 and d = 1, X 3 when X is a sulfur atom, c = 2 and d = 0 Y 4 ~Y 7 each independently represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms or -O - (M 4 F+ ) f ,M 4 F+ represents a proton, a metal cation or an onium cation, F represents the valence of the cation, f represents a number such that F×f = 1, the hydrocarbon group optionally has at least one selected from the group consisting of a heteroatom and a halogen atom, and when the hydrocarbon group has 3 or more carbon atoms, it optionally has a branched or cyclic structure In general formula (4), R 6 ~R 9 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, the hydrocarbon group optionally having at least one selected from the group consisting of a heteroatom and a halogen atom, and when the hydrocarbon group has 3 or more carbon atoms, optionally having a branched or cyclic structure, and the alkoxy group optionally having a halogen atom.

15. A non-aqueous sodium-ion battery, comprising at least: a positive electrode, a negative electrode, and an electrolyte for a non-aqueous sodium-ion battery according to any one of claims 1 to 10.

16. A method for manufacturing a non-aqueous sodium-ion battery, comprising the following steps: A step of preparing an electrolyte for a non-aqueous sodium-ion battery according to any one of claims 1 to 10; A step of filling the electrolyte for a non-aqueous sodium-ion battery into an empty battery cell having at least a positive electrode and a negative electrode.

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