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JP-2026076364-A - Non-aqueous electrolytes and non-aqueous electrolyte batteries

JP2026076364AJP 2026076364 AJP2026076364 AJP 2026076364AJP-2026076364-A

Abstract

[Problem] To provide a non-aqueous electrolyte that can suppress the amount of gas generated when a non-aqueous electrolyte battery is stored at high temperature, a non-aqueous electrolyte battery equipped with the non-aqueous electrolyte, and a compound used in the non-aqueous electrolyte. [Solution] A non-aqueous electrolyte for a non-aqueous electrolyte battery having a positive electrode and a negative electrode capable of intercalating and releasing metal ions, characterized in that the non-aqueous electrolyte contains a compound represented by formula (1) together with an alkali metal salt and a non-aqueous solvent. In formula (1), R1 is a hydrogen atom, a halogen atom, or a substituted/unsubstituted monovalent hydrocarbon group; R2 is a hydrogen atom, a substituted/unsubstituted monovalent hydrocarbon group, or a substituted alkoxy group; X1 is a substituted/unsubstituted divalent hydrocarbon group; n1 is 2 or 3; p1 is an integer from 0 to 2; q1 is an integer from 1 to 3, p1 + q1 = 2 or 3; two of R1 and X1 are bonded to each other to form a ring; and A1 is a divalent or trivalent group of atoms represented by a specific formula. [Selection Diagram] None

Inventors

  • 中澤 英司
  • 玉井 花穂

Assignees

  • 三菱ケミカル株式会社
  • ＭＵアイオニックソリューションズ株式会社

Dates

Publication Date
20260511
Application Date
20260219
Priority Date
20200519

Claims (6)

  1. A non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of intercalating and releasing metal ions, and a non-aqueous electrolyte, The negative electrode contains a negative electrode active material which contains a material that contains a metallic element and/or a metalloid element that can be alloyed with Li, The negative electrode further contains a carbon-based material, wherein the carbon-based material is graphite particles. The material containing a metallic element and/or metalloid element that can be alloyed with Li is a metallic particle that can be alloyed with Li, The ratio of metal particles that can be alloyed with Li to the total of metal particles that can be alloyed with Li and graphite particles is 0.1% by mass or more and 99% by mass or less. A non-aqueous electrolyte battery characterized in that the non-aqueous electrolyte contains an alkali metal salt, a non-aqueous solvent, and a compound represented by the following general formula (4). (In general formula (4), R3 represents a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group; R4 represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, or an optionally substituted alkoxy group; X2 represents an optionally substituted divalent hydrocarbon group; n2 represents an integer from 1 to 3; p2 represents an integer from 0 to 2, q2 represents an integer from 1 to 3, and p2 + q2 = 2 or 3; two of R3 and X2 may be bonded to each other to form a ring; A2 is a divalent or trivalent atomic group represented by the following general formula (5-1), or a trivalent atomic group represented by the following general formula (6-1).) (In general formula (5-1), Z 3 represents a carbon atom, a sulfur atom, a phosphorus atom, or a boron atom; Y 102 represents an oxygen atom or a sulfur atom; Y 10 , Y 11 , and Y 12 each independently represent a single bond, an oxygen atom, a sulfur atom, or NR 102 ; R 102 represents a hydrogen atom or a monovalent hydrocarbon group; r 5 is 1 when Z 3 is a carbon atom, 0, 1, or 2 when Z 3 is a sulfur atom, 0 or 1 when Z 3 is a phosphorus atom, and 0 when Z 3 is a boron atom. r 6 is 0 when Z 3 is a carbon atom or a sulfur atom, and 1 when Z 3 is a phosphorus atom or a boron atom; * indicates the bonding site with R3 or X2 in the general formula (4) above. However, when Z3 is a sulfur atom and r5 is 2, Y10 and Y11 cannot both be single bonds. (In general formula (6-1), Y 13 , Y 14 , and Y 15 each independently represent an oxygen atom, a sulfur atom, or NR 202 ; R 202 represents a hydrogen atom or a monovalent hydrocarbon group; and * indicates the bonding site with R 3 or X 2 in general formula (4).)
  2. The non-aqueous electrolyte battery according to claim 1, wherein A2 in formula (4) is a divalent or trivalent atomic group represented by formula (5-1).
  3. The non-aqueous electrolyte battery according to claim 1, wherein the divalent or trivalent atomic group represented by the general formula (5-1) is a divalent group having a ketone structure, a divalent group having a carbonate structure, a divalent group having a carboxylic acid ester structure, a divalent group having a sulfonic acid ester structure, a divalent group having a sulfite ester structure, a divalent group having a sulfinic acid ester structure, a trivalent group having a phosphonic acid ester structure, or a trivalent group having a phosphate ester structure.
  4. The non-aqueous electrolyte battery according to claim 1, wherein Z3 in the general formula (5-1) is a carbon atom.
  5. The non-aqueous electrolyte battery according to claim 1, wherein the compound represented by formula (4) is one of the following compounds: compound 1, compound 2, compound 3, compound 4, compound 5, compound 6, compound 7, compound 9, or compound 13.
  6. The non-aqueous electrolyte battery according to claim 1 or 2, wherein the ratio of metal particles that can be alloyed with Li to the total of the metal particles that can be alloyed with Li and the graphite particles is 0.1% by mass or more and 50% by mass or less.

Description

This invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery, and more specifically, to a non-aqueous electrolyte containing a specific compound in a specific amount, and to a non-aqueous electrolyte battery using this non-aqueous electrolyte. Non-aqueous electrolyte batteries, such as lithium-ion secondary batteries, are being put into practical use in a wide range of applications, including power supplies for so-called consumer small devices such as smartphones and laptops, as well as on-board power supplies for electric vehicles. Numerous studies have been conducted in the fields of active materials for the positive and negative electrodes, and additives for the non-aqueous electrolyte, as means of improving the battery characteristics of non-aqueous electrolyte batteries. For example, Patent Document 1 discloses a specific organosilicon compound having an organic polar group that, when used as a liquid electrolyte solvent, can provide a lithium-ion battery that is given effects such as improved thermal stability at high temperatures and improved safety due to an increase in the electrolyte flash point. Patent Document 2 discloses a study on improving cycle characteristics and resistance increase rate by adding a monofluorosilane compound having a specific organic group. Patent documents 3 and 4 disclose studies on improving the high-temperature cycle capacity retention rate by adding specific organosilicon compounds having organic groups such as cyano groups, isocyanate groups, or isothiocyanate groups in their structure to a non-aqueous electrolyte. Patent Document 5 discloses a study on improving the volume retention rate and resistance increase during long-term use and high-temperature storage by adding a specific fluorosilane compound to a non-aqueous electrolyte. Special table 2017-538667 publicationInternational Publication No. 2018/220997Special table 2016-520647 publicationJapanese Patent Publication No. 2018-46021Japanese Patent Publication No. 2009-004352 The embodiments of the present invention will be described in detail below. The following embodiments are examples (representative examples) of the present invention, and the present invention is not limited thereto. Furthermore, the present invention can be modified and implemented as appropriate without departing from its spirit. In this specification, any notation represented by "~" indicates a range that includes the numbers before and after it. Furthermore, in this specification, when describing two or more subjects together, the terms "independently" or "independently" are used to mean that those two or more subjects may be the same or different. <A. First Embodiment> <A1. Non-aqueous electrolyte> The non-aqueous electrolyte according to the first embodiment of the present invention contains a compound represented by the general formula (1) described below. The mechanism by which using a non-aqueous electrolyte containing the compound represented by general formula (1) enhances the suppression of gas generation during high-temperature storage of non-aqueous electrolyte batteries is not clear, but it is presumed to be as follows. Compounds represented by general formula (1) have a divalent or trivalent atomic group within the molecule, each containing at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and boron. Because this atomic group is a polar group, compounds represented by formula (1) tend to interact with carbon on the surface of the negative electrode active material and localize near the negative electrode active material surface. Furthermore, compounds represented by general formula (1) have a structure in which two or more fluorine (F) atoms are bonded to a silicon (Si) atom within the molecule. When two or more F atoms are bonded to a Si atom, the electron density of the Si atom decreases significantly compared to when there is only one F atom. As a result, the reactivity of the Si atom in compounds represented by general formula (1) increases, allowing for easier progress of processes such as electrochemical reduction and reactions with reductive decomposition products of the electrolyte. This facilitates the formation of an insulating film on the negative electrode active material and, for example, favorably modifies the surface when Si is used as the negative electrode active material. Furthermore, it is presumed that the compound represented by general formula (1) also concentrates on the positive electrode surface, reacts with electrochemical oxidation and oxidative decomposition products of the electrolyte, and forms an insulating film similar to that on the negative electrode. Based on the above, the inventors believe that the compound represented by general formula (1) contributes to suppressing gas generation during high-temperature storage. <A1-1. Compounds represented by general formula (1)> A non-aqueous electrolyte according to one embodiment of the present inventi