JP6866067B2 - Non-aqueous electrolyte and storage device using it - Google Patents

Description

The present invention relates to a non-aqueous electrolytic solution capable of improving electrochemical properties in a wide temperature range and a power storage device using the same.

In recent years, power storage devices, particularly lithium secondary batteries, have been widely used for small electronic devices such as mobile phones and notebook computers, electric vehicles, and power storage. Since these electronic devices and automobiles may be used in a wide temperature range such as a high temperature in midsummer or a low temperature in extremely cold, it is required to improve the electrochemical characteristics in a well-balanced manner in a wide temperature range.
In particular, in order to prevent global warming, _{there is an urgent need to reduce CO 2} emissions, and among environmentally friendly vehicles equipped with power storage devices consisting of power storage devices such as lithium secondary batteries and capacitors, hybrid electric vehicles ( HEV), plug-in hybrid electric vehicles (PHEV), and battery electric vehicles (BEV) are required to be widely used at an early stage. Due to the long travel distances of automobiles, they can be used in a wide range of temperatures, from extremely hot tropical regions to extremely cold regions. Therefore, in particular, these in-vehicle power storage devices are required not to deteriorate their electrochemical characteristics even when used in a wide temperature range from high temperature to low temperature.
In the present specification, the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.

The lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium, a non-aqueous electrolytic solution composed of a lithium salt and a non-aqueous solvent, and examples of the non-aqueous solvent include ethylene carbonate (EC). A carbonate such as propylene carbonate (PC) is used.
Further, as the negative electrode, metallic lithium, a metal compound capable of occluding and releasing lithium (single metal, oxide, alloy with lithium, etc.) and a carbon material are known, and in particular, lithium can be occluded and released. Lithium secondary batteries using carbon materials such as occlusion, artificial graphite, and natural graphite have been widely put into practical use.

For example, a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as a negative electrode material is a decomposition product generated by reduction decomposition of a solvent in a non-aqueous electrolytic solution on the negative electrode surface during charging. It has been found that the gas interferes with the desired electrochemical reaction of the battery, resulting in reduced cycle characteristics. Further, when the decomposition products of the non-aqueous solvent are accumulated, the lithium can not be smoothly stored and released into the negative electrode, and the electrochemical characteristics when used in a wide temperature range tend to be deteriorated.
Furthermore, lithium secondary batteries that use lithium metal or its alloy, a single metal such as tin or silicon, or an oxide as the negative electrode material have a high initial capacity, but become finer during the cycle, so they can be used as the negative electrode for carbon materials. It is known that the reductive decomposition of non-aqueous solvents occurs at an accelerated rate, and the battery performance such as battery capacity and cycle characteristics is significantly reduced. In addition, if these negative electrode materials are pulverized or the decomposition products of non-aqueous solvents are accumulated, the storage and release of lithium into the negative electrode cannot be performed smoothly, and the electrochemical characteristics are likely to deteriorate when used in a wide temperature range. ..

On the other hand, in _{the lithium secondary battery using, for example, LiCoO 2} , LiMn ₂ O ₄ , LiNiO ₂ , LiFePO ₄ or the like as the positive electrode, the non-aqueous solvent in the non-aqueous electrolyte solution is charged and the positive electrode material and the non-aqueous electrolyte solution are used. At the interface between the two, the decomposition products and gases generated by the partial oxidative decomposition of the battery inhibit the desired electrochemical reaction of the battery, which also causes a decrease in the electrochemical properties when used in a wide temperature range. I know.

As described above, the decomposition products and gases when the non-aqueous electrolyte solution decomposes on the positive electrode and the negative electrode hinder the movement of lithium ions and cause the battery to swell, resulting in deterioration of battery performance. In spite of such a situation, electronic devices equipped with lithium secondary batteries are becoming more and more multifunctional, and power consumption is increasing. Therefore, the capacity of lithium secondary batteries is increasing more and more, and the volume occupied by the non-aqueous electrolyte solution in the battery is becoming smaller, such as increasing the density of electrodes and reducing the wasted space volume in the battery. .. Therefore, even a small amount of decomposition of the non-aqueous electrolyte solution tends to reduce the electrochemical characteristics when used in a wide temperature range.

Patent Document 1 discloses 1,3-dioxolane-2-onylmethylallyl sulfonate as one of the compounds in which a cyclic carbonate group and a sulfonate group are bonded using an alkylene group, and it should be added to an electrolytic solution. It has been suggested that the cycle capacity retention rate of the battery is improved.

International Publication No. 2008/035928

The present invention provides a non-aqueous electrolytic solution capable of improving electrochemical properties in a wide temperature range, a power storage device using the same, and a novel (2-oxo-1,3-dioxolane-4-yl) oxy compound. The purpose is.

As a result of detailed examination of the performance of the non-aqueous electrolyte solution of the prior art, the present inventors have found that the secondary battery using the non-aqueous electrolyte solution of Patent Document 1 has cycle characteristics at high temperature and after high temperature storage. The actual situation is that sufficient effects have not been obtained for the problem of improving the electrochemical characteristics in a wide temperature range such as the low temperature discharge characteristics of the above.
Therefore, the present inventors have conducted intensive studies to solve the above problems, and by containing one or more specific compounds in a non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a non-aqueous solvent, a wide temperature can be obtained. We have found that the electrochemical characteristics of the power storage device, particularly the electrochemical characteristics of the lithium battery, can be improved within the range, and completed the present invention. The effect of improving the low temperature discharge characteristics after high temperature storage is not suggested at all in Patent Document 1.

That is, the present invention provides the following (1), (2) and (3).
(1) In a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, one or more (2-oxo-1,3-dioxolane-4-yl) oxy compounds represented by the following general formula (I) are used. A non-aqueous electrolyte solution containing.

（式中、Ｒ^１は、水素原子、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、−ＯＣ（＝Ｏ）−Ｒ^４、−ＯＳ（＝Ｏ）_２−Ｒ^５、又は−ＯＰ（＝Ｏ）（−Ｒ^６）−Ｒ^７を示す。Ｒ^２及びＲ^３は、水素原子、ハロゲン原子、又は少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数１〜６のアルキル基を示し、ｎは１〜３の整数を示す。ｎが１の場合、Ｌ^１は−Ｃ（＝Ｏ）−Ｒ^４、−Ｓ（＝Ｏ）_２−Ｒ^５、又は−Ｐ（＝Ｏ）（−Ｒ^６）−Ｒ^７を示し、ｎが２の場合、Ｌ^１は−Ｃ（＝Ｏ）Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）_２−、又は−Ｐ（＝Ｏ）（−Ｒ^６）−を示し、ｎが３の場合、Ｌ^１は−Ｐ（＝Ｏ）（−）_２を示す。Ｒ^４は、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、又は少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数２〜６のアルコキシカルボニル基を示す。Ｒ^５は、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、又は少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルコキシ基を示す。また、Ｒ^６及びＲ^７は、それぞれ独立して、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数１〜６のアルコキシ基、又は少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリールオキシ基を示す。）

(In the formula, R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, and a carbon number of carbon atoms. An alkenyl group of 2 to 6, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and at least one hydrogen atom being substituted with a halogen atom. An aryl group having 6 to 12 carbon atoms, which may be formed,: -OC (= O) -R ⁴ , -OS (= O) _2- R ⁵ , or -OP (= O) ( ^{-R 6} ) -R ⁷ . R ² and R ³ represent alkyl groups having 1 to 6 carbon atoms in which a hydrogen atom, a halogen atom, or at least one hydrogen atom may be substituted with a halogen atom, and n represents an integer of 1 to 3. When n is 1, L ¹ indicates -C (= O) -R ⁴ , -S (= O) _2- R ⁵ , or -P (= O) ( ^{-R 6} ) -R ⁷ , and n When is 2, L ¹ indicates −C (= O) C (= O) −, −S (= O) ₂₋ , or −P (= O) (−R ⁶ ) −, and n is 3. In the case, L ¹ indicates −P (= O) (−) _2. R ⁴ is an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and 3 to 6 carbon atoms. A cycloalkyl group of 6, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, at least 1 Indicates an aryl group having 6 to 12 carbon atoms in which one hydrogen atom may be substituted with a halogen atom, or an alkoxycarbonyl group having 2 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom. ^{Reference numeral 5} denotes a halogen atom, an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and carbon. Alkinyl groups of number 2 to 6, aralkyl groups having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with halogen atoms, and 6 to 6 carbon atoms in which at least one hydrogen atom may be substituted with halogen atoms. Twelve aryl groups, or alkoxy groups having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, are shown. Further, R ⁶ and R ⁷ are independently halogen atoms, at least. One hydrogen atom may be replaced with a halogen atom 1 to 1 carbon atoms 6 shows an alkoxy group or an aryloxy group having 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom. )

(2) In a power storage device including a positive electrode, a negative electrode, and a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to the above (1). A characteristic power storage device.

(3) (2-oxo-1,3-dioxolane-4-yl) oxy compound represented by the following general formula (II)

（式中、Ｒ^８は、水素原子、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、−ＯＣ（＝Ｏ）−Ｒ^９、−ＯＳ（＝Ｏ）_２−Ｒ^５、又は−ＯＰ（＝Ｏ）（−Ｒ^６）−Ｒ^７を示す。Ｒ^２及びＲ^３は、水素原子、ハロゲン原子、又は少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数１〜６のアルキル基を示し、ｎは１〜３の整数を示す。ｎが１の場合、Ｌ^２は−Ｃ（＝Ｏ）−Ｒ^９、−Ｓ（＝Ｏ）_２−Ｒ^５、又は−Ｐ（＝Ｏ）（−Ｒ^６）−Ｒ^７を示し、ｎが２の場合、Ｌ^２は−Ｃ（＝Ｏ）Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）_２−、又は−Ｐ（＝Ｏ）（−Ｒ^６）−を示し、ｎが３の場合、Ｌ^２は−Ｐ（＝Ｏ）（−）_２を示す。Ｒ^９は、少なくとも１つの水素原子がハロゲン原子で置換された炭素数１〜６のハロアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、又は少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数２〜６のアルコキシカルボニル基を示す。Ｒ^５は、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、又は少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルコキシ基を示す。また、Ｒ^６及びＲ^７は、それぞれ独立して、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数１〜６のアルコキシ基、又は少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリールオキシ基を示す。）

(In the formula, R ⁸ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, and a carbon number of carbon atoms. An alkenyl group of 2 to 6, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and at least one hydrogen atom being substituted with a halogen atom. An aryl group having 6 to 12 carbon atoms, which may be formed,: -OC (= O) -R ⁹ , -OS (= O) _2- R ⁵ , or -OP (= O) ( ^{-R 6} ) -R ⁷ . R ² and R ³ represent alkyl groups having 1 to 6 carbon atoms in which a hydrogen atom, a halogen atom, or at least one hydrogen atom may be substituted with a halogen atom, and n represents an integer of 1 to 3. When n is 1, L ² indicates -C (= O) -R ⁹ , -S (= O) _2- R ⁵ , or -P (= O) ( ^{-R 6} ) -R ⁷ , and n When is 2, L ² indicates −C (= O) C (= O) −, −S (= O) ₂₋ , or −P (= O) (−R ⁶ ) −, and n is 3. In the case, L ² indicates −P (= O) (−) _2. R ⁹ is a haloalkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is replaced with a halogen atom, and a cyclo having 3 to 6 carbon atoms. An alkyl group, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and at least one hydrogen atom may be substituted with a halogen atom. An aryl group having 6 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms in which at least one hydrogen atom may be substituted with ^{a halogen atom. R 5} is a halogen atom, at least one hydrogen atom. An alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and at least one hydrogen. An aralkyl group having 7 to 13 carbon atoms in which the atom may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, or at least one hydrogen atom. It represents an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. Further, R ⁶ and R ⁷ are independently each of a halogen atom, even if at least one hydrogen atom is substituted with a halogen atom. A good alkoxy group with 1 to 6 carbon atoms, or at least 1 It shows an aryloxy group having 6 to 12 carbon atoms in which one hydrogen atom may be substituted with a halogen atom. )

The partial structure of −P (= O) (−) ₂ described in the present specification means a structure represented by the following general formula (III).

According to the present invention, a non-aqueous electrolyte solution capable of improving the electrochemical characteristics of a power storage device in a wide temperature range, particularly low temperature discharge characteristics after high temperature storage, a power storage device such as a lithium battery using the same, and a novel (2). −oxo-1,3-dioxolane-4-yl) oxy compounds can be provided.

The present invention relates to a non-aqueous electrolytic solution and a power storage device using the same.

[Non-aqueous electrolyte]
The non-aqueous electrolyte solution of the present invention is a non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a non-aqueous solvent, and is represented by the general formula (I) in the non-aqueous electrolyte solution (2-oxo-1,3). A non-aqueous electrolyte solution containing at least one −dioxolan-4-yl) oxy compound.

The reason why the non-aqueous electrolytic solution of the present invention can significantly improve the electrochemical characteristics of the power storage device in a wide temperature range is not always clear, but it is considered as follows.
As described in the general formula (I), the compound used in the present invention is a cyclic carbonate in which a polar group is directly bonded to a ring without an alkylene group. Therefore, it is more electrochemically decomposed than 1,3-dioxolan-2-onylmethylallyl sulfonate, which is a compound in which a cyclic carbonate group and a sulfonate group which is a polar group are bonded via an alkylene group described in Patent Document 1. A dense and highly heat-resistant film is formed on the positive electrode and the negative electrode. Therefore, it is considered that the electrochemical characteristics in a wide temperature range such as the low temperature discharge characteristics after high temperature storage can be improved.

The compound contained in the non-aqueous electrolytic solution of the present invention is an oxy compound represented by the following general formula (I) (2-oxo-1,3-dioxolan-4-yl).

（式中、Ｒ^１は、水素原子、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、−ＯＣ（＝Ｏ）−Ｒ^４、−ＯＳ（＝Ｏ）_２−Ｒ^５、又は−ＯＰ（＝Ｏ）（−Ｒ^６）−Ｒ^７を示す。Ｒ^２及びＲ^３は、水素原子、ハロゲン原子、又は少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数１〜６のアルキル基を示し、ｎは１〜３の整数を示す。ｎが１の場合、Ｌ^１は−Ｃ（＝Ｏ）−Ｒ^４、−Ｓ（＝Ｏ）_２−Ｒ^５、又は−Ｐ（＝Ｏ）（−Ｒ^６）−Ｒ^７を示し、ｎが２の場合、Ｌ^１は−Ｃ（＝Ｏ）Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）_２−、又は−Ｐ（＝Ｏ）（−Ｒ^６）−を示し、ｎが３の場合、Ｌ^１は−Ｐ（＝Ｏ）（−）_２を示す。Ｒ^４は、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、又は少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数２〜６のアルコキシカルボニル基を示す。Ｒ^５は、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、又は少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルコキシ基を示す。また、Ｒ^６及びＲ^７は、それぞれ独立して、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数１〜６のアルコキシ基、又は少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリールオキシ基を示す。）

(In the formula, R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, and a carbon number of carbon atoms. An alkenyl group of 2 to 6, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and at least one hydrogen atom being substituted with a halogen atom. An aryl group having 6 to 12 carbon atoms, which may be formed,: -OC (= O) -R ⁴ , -OS (= O) _2- R ⁵ , or -OP (= O) ( ^{-R 6} ) -R ⁷ . R ² and R ³ represent alkyl groups having 1 to 6 carbon atoms in which a hydrogen atom, a halogen atom, or at least one hydrogen atom may be substituted with a halogen atom, and n represents an integer of 1 to 3. When n is 1, L ¹ indicates -C (= O) -R ⁴ , -S (= O) _2- R ⁵ , or -P (= O) ( ^{-R 6} ) -R ⁷ , and n When is 2, L ¹ indicates −C (= O) C (= O) −, −S (= O) ₂₋ , or −P (= O) (−R ⁶ ) −, and n is 3. In the case, L ¹ indicates −P (= O) (−) _2. R ⁴ is an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and 3 to 6 carbon atoms. A cycloalkyl group of 6, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, at least 1 Indicates an aryl group having 6 to 12 carbon atoms in which one hydrogen atom may be substituted with a halogen atom, or an alkoxycarbonyl group having 2 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom. ^{Reference numeral 5} denotes a halogen atom, an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and carbon. Alkinyl groups of number 2 to 6, aralkyl groups having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with halogen atoms, and 6 to 6 carbon atoms in which at least one hydrogen atom may be substituted with halogen atoms. Twelve aryl groups, or alkoxy groups having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, are shown. Further, R ⁶ and R ⁷ are independently halogen atoms, at least. One hydrogen atom may be replaced with a halogen atom 1 to 1 carbon atoms 6 shows an alkoxy group or an aryloxy group having 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom. )

As ^{a specific example of R 1} , a halogen atom such as a hydrogen atom, a fluorine atom, a chlorine atom, or a bromine atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, or n- Linear alkyl group such as hexyl group, iso-propyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, tert-butyl group, or branched alkyl group such as tert-amyl group, fluoro Methyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3 , 3-Difluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, or 2,2,3,3,3-pentafluoropropyl group, etc. Cycloalkyl group such as alkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, or cycloheptyl group, vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, 1-propene -2-yl group, 2-butene-1-yl group, 3-buten-1-yl group, 4-penten-1-yl group, 5-hexene-1-yl group, 1-propen-2-yl group , 1-buten-2-yl group, or alkenyl group such as 2-methyl-2-propen-1-yl group, ethynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 4-heptinyl group , 1-Methyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-methyl-3-butynyl group, or alkynyl group such as 1-methyl-4-heptinyl group, benzyl group, 4-methyl Benzyl group, 4-tert-butylbenzyl group, 4-fluorobenzyl group, 4-chlorobenzyl group, 1-phenylethane-1-yl group, 2-phenylethane-1-yl group, or 3-phenylpropane-1 -Aralkyl group such as yl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4 -Fluorophenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethyl Phenyl group, 2,6-difluorofe Nyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, or aryl group such as perfluorophenyl, acetyloxy group, propionyloxy Group, fluorosulfonyloxy group, methanesulfonyloxy group, vinylsulfonyloxy group, difluorophosphoryl group, dimethoxyphosphoryl group, diethoxyphosphoryl group and the like are preferably mentioned, and among them, hydrogen atom, fluorine atom, methyl group and ethyl group. , N-propyl group, n-butyl group, n-pentyl group, n-hexyl group, iso-propyl group, sec-butyl group, 2-pentyl group, tert-butyl group, tert-amyl group, trifluoromethyl group , 2-fluoroethyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, 1-propen-2-yl group, ethynyl group, 2-propynyl group, 2-butynyl group, benzyl group, 4-methylbenzyl group, phenyl group, 4-methylphenyl group, acetyloxy group, propionyloxy group, fluorosulfonyloxy group, methanesulfonyloxy group, vinylsulfonyloxy group , Difluorophosphoryl group, dimethoxyphosphoryl group, or diethoxyphosphoryl group, preferably hydrogen atom, fluorine atom, methyl group, ethyl group, n-propyl group, iso-propyl group, tert-butyl group, trifluoromethyl group, cyclo Propyl group, cyclohexyl group, vinyl group, 1-propen-1-yl group, 1-propen-2-yl group, ethynyl group, 2-propynyl group, phenyl group, 4-methylphenyl group, acetyloxy group, fluorosulfonyl group More preferably, an oxy group, a methanesulfonyloxy group, a vinylsulfonyloxy group, a difluorophosphoryl group, a dimethoxyphosphoryl group, or a diethoxyphosphoryl group.

Specific examples of R ² and R ³ include halogen atoms such as hydrogen atom, fluorine atom, chlorine atom, and bromine atom, methyl group, ethyl group, n-propyl group, n-butyl group, and n-pentyl group. Alternatively, a straight chain alkyl group such as an n-hexyl group, an iso-propyl group, a sec-butyl group, a 2-pentyl group, a pentan-3-yl group, a tert-butyl group, or a branched chain such as a tert-amyl group. Alkyl group, or fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3 -Chloropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, or 2,2,3,3,3-pentafluoro Alkyl halide groups such as propyl group are preferably mentioned, and among them, hydrogen atom, fluorine atom, chlorine atom, methyl group, ethyl group, n-propyl group, n-butyl group, iso-propyl group and sec-butyl group. , Tert-butyl group, or trifluoromethyl group is preferable, and hydrogen atom, fluorine atom, or methyl group is more preferable.

Wherein, ^{R 4} is a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group, or n- hexyl linear alkyl group such as, iso- propyl, sec- butyl group, Branched alkyl groups such as 2-pentyl group, 3-pentyl group, tert-butyl group, or tert-amyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl Group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, or Cycloalkyl group such as 2,2,3,3,3-pentafluoropropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, or cycloalkyl group such as cycloheptyl group, vinyl group, 1-propene -1-Il group, 2-propen-1-yl group, 2-butene-1-yl group, 3-butene-1-yl group, 4-penten-1-yl group, 5-hexene-1-yl group , 1-propen-2-yl group, 1-buten-2-yl group, or alkenyl group such as 2-methyl-2-propen-1-yl group, ethynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 4-heptinyl group, 1-methyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-methyl-3-butynyl group, 1-methyl-4-pentynyl group, etc. Aralkyl groups such as alkynyl group, benzyl group, 4-methylbenzyl group, 1-phenylethane-1-yl group, 2-phenylethane-1-yl group, or 3-phenylpropan-1-yl group, phenyl group, 2-Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl Group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenyl group, 2,6-difluorophenyl group, 3,5-Difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, or aryl group such as perfluorophenyl, methoxycarbonyl group, ethoxycarbonyl group and the like. Alkoxycarboni Lu groups are preferred, among which methyl group, ethyl group, n-propyl group, iso-propyl group, tert-butyl group, fluoromethyl group, chloromethyl group, trifluoromethyl group, 2-fluoroethyl group, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, vinyl group, 1-propen-1-yl group, ethynyl group, 2-propynyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl Group, 4-methylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, methoxycarbonyl group, or ethoxycarbonyl group is preferable, and methyl group, ethyl group, iso-propyl group, trifluoromethyl group, cyclo A propyl group, a cyclohexyl group, a vinyl group, a 1-propen-2-yl group, an ethynyl group, a phenyl group, a 4-fluorophenyl group, a 4-trifluorophenyl group, a methoxycarbonyl group, or an ethoxycarbonyl group are more preferable.

Wherein, R ⁵ is a hydrogen atom, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl or n- hexyl group or the like, Branched alkyl groups such as linear alkyl group, iso-propyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, fluoromethyl group, chloromethyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group and other alkyl halide groups, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, Cycloalkyl group such as cycloheptihexyl group, vinyl group, alkenyl group such as 1-propen-1-yl group, 2-propen-1-yl group, alkynyl group such as ethynyl group and 2-propynyl group, benzyl group , 4-Methylbenzyl group, 1-Phenylethane-1-yl group, 2-Phenylethane-1-yl group, or 3-phenylpropan-1-yl group and other aralkyl groups, or phenyl group, 2-methylphenyl. Group, 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group, 2-fluorophenyl group, 2-chlorophenyl group, 2-bromophenyl group, 4-fluorophenyl group, 4-chlorophenyl group, Alternatively, aryl groups such as 4-trifluoromethylphenyl group, methoxy group, or alkoxy groups such as ethoxy group are preferably mentioned, and among them, fluorine atom, methyl group, ethyl group, n-propyl group, trifluoromethyl group, etc. Cyclopropyl group, cyclobutyl group, cyclohexyl group, vinyl group, ethynyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group , Methoxy group, or ethoxy group is preferable, fluorine atom, methyl group, ethyl group, propyl group, hexyl group, iso-propyl group, trifluoromethyl group, cyclohexyl group, vinyl group, ethynyl group, phenyl group, 2-methyl Further preferred are a phenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-fluorophenyl group, a 4-trifluoromethylphenyl group, or a methoxy group.

As ^{specific examples of R 6} and R ⁷ , halogen atoms such as fluorine atom, chlorine atom or bromine atom, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group or n- A branched chain such as a linear alkyloxy group such as a hexyloxy group, an iso-propoxy group, a sec-butoxy group, a 2-pentoxy group, a pentan-3-yloxy group, a tert-butoxy group, or a tert-amyloxy group. Alkyloxy group, 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3,3-difluoropropoxy group, 3 , 3,3-Trifluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, or alkyl halide group such as 2,2,3,3,3-pentafluoropropoxy group, or phenoxy group, 2 -Methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 4-tert-butylphenoxy group, 2-fluorophenoxy group, 2-chlorophenoxy group, 2-bromophenoxy group, 4-fluorophenoxy group, 4 Preferable examples include aryl groups such as −chlorophenoxy group and 4-trifluoromethylphenoxy group, among which fluorine atom, chlorine atom, methoxy group, ethoxy group, n-propoxy group, n-butoxy group and iso-propoxy. Group, sec-butoxy group, tert-butoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, or 2,2,3 , 3,3-Pentafluoropropoxy group, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-fluorophenoxy group 4-fluorophenoxy group, or 4-trifluoromethylphenoxy group Such as an aryl group is preferable, and a fluorine atom, a methoxy group, an ethoxy group, a 2,2-difluoroethoxy group, a 2,2,2-trifluoroethoxy group, or a phenoxy group is more preferable.

Specific preferred examples of the general formula (I) include the following compounds.

When n is 1 and L ¹ is -C (= O) -R ⁴ .

When n is 2 and L ¹ is -C (= O) C (= O)-

When n is 1 and L ¹ is -S (= O) _2- R ⁵

When n is 2 and L ¹ is −S (= O) ₂₋

When n is 1 and L ¹ is -P (= O) ( ^{-R 6} ) -R ⁷ .

When n is 2 and L ¹ is -P (= O) (-R ⁶ )-

When n is 3 and L ¹ is -P (= O) (-) ₂ .

Among the above compounds, A1 to A10, A14 to A19, B1 to B3, C1 to C9, C11 to C20, C24 to C27, C32, C34 to C36, D1 to D3, E1 to E3, E5 to E8, E10 to E13, Compounds having the structural formulas of E15, F1 to F3, F5 to F7, F9 to F11, or G1 to G3 are preferable, and A1, A2, A4, A7, A8, A16 to A18, B1, B2, C1 to C3, C7. , C9, C11, C14, C17 to C19, C35, C36, D1, D2, E1, E2, E6, E7, E11, E12, F1, F2, F5, F6, F9, F10, G1 or G2. The compound having is more preferable, 2-oxo-1,3-dioxolan-4-yl acetate (structural formula A1), 2-oxo-1,3-dioxolan-4-yl 2,2,2-trifluoroacetate (structure). Formula A4), 2-oxo-1,3-dioxolane-4-yl acrylate (structural formula A7), 2-oxo-1,3-dioxolan-4-yl methacrylate (structural formula A8), methyl (2-oxo-). 1,3-Dioxolane-4-yl) oxalate (structural formula A16), ethyl (2-oxo-1,3-dioxolan-4-yl) oxalate (structural formula A17), bis (2-oxo-1,3-yl) Dioxolan-4-yl) oxalate (structural formula B1), 2-oxo-1,3-dioxolan-4-yl sulfolofluoridet (structural formula C1), 2-oxo-1,3-dioxolan-4-yl methane Sulfonate (Structural Formula C2), 2-oxo-1,3-dioxolane-4-yltrifluoromethanesulfonate (Structural Formula C7), 2-oxo-1,3-dioxolane-4-ylethenesulfonate (Structural Formula C9), Methyl (2-oxo-1,3-dioxolane-4-yl) sulfate (structural formula C17), 5-fluoro-2-oxo-1,3-dioxolane-4-ylmethanesulfonate (structural formula C18), 5- Methyl-2-oxo-1,3-dioxolane-4-ylmethanesulfonate (structural formula C19), 2-oxo-1,3-dioxolane-4,5-diyldimethanesulfonate (structural formula C35), bis (2) -Oxo-1,3-dioxolane-4-yl) sulfate (structural formula D1), 2-oxo-1,3-dioxolan-4-yl phosphorodifluoridate (structural formula E1), dimethyl (2-oxo-1) ， 3-Geo Xolan-4-yl) phosphate (structural formula E6) or diethyl (2-oxo-1,3-dioxolan-4-yl) phosphate (structural formula E11) is particularly preferred.

The (2-oxo-1,3-dioxolane-4-yl) oxy derivative compound of the present invention can be synthesized by the following two methods, but is not limited to this method.
(A) Reaction method of alkyl halide and potassium carboxylic acid salt Chem. Ber. , 1970, 112 , 148, obtained by reacting an alkyl halide with a potassium carboxylic acid salt in a solvent.
(B) Reaction method of alkyl halide and silver sulfonic acid salt It is obtained by reacting alkyl halide and silver sulfonic acid salt in a solvent by the method described in Synthesis, 1971, 150.

In the non-aqueous electrolytic solution of the present invention, the content of the (2-oxo-1,3-dioxolan-4-yl) oxy derivative compound represented by the general formula (I) contained in the non-aqueous electrolytic solution is determined. It is preferably 0.01 to 10% by mass in the non-aqueous electrolyte solution. If the content is 10% by mass or less, there is little possibility that an excessive film is formed on the electrode and the low temperature characteristics are deteriorated, and if it is 0.01% by mass or more, the film is sufficiently formed and the temperature is wide. The above range is preferable because the effect of improving the electrochemical properties in the range is enhanced. The content is more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more in the non-aqueous electrolytic solution. Further, the upper limit thereof is more preferably 5% by mass or less, further preferably 3% by mass or less.

In the non-aqueous electrolyte solution of the present invention, the (2-oxo-1,3-dioxolane-4-yl) oxy derivative compound represented by the general formula (I) is referred to as the non-aqueous solvent, electrolyte salt, and the like described below. By combining these additives, the unique effect of synergistically improving the electrochemical properties over a wide temperature range is exhibited.

[Non-aqueous solvent]
As the non-aqueous solvent used in the non-aqueous electrolytic solution of the present invention, one or more selected from cyclic carbonates, chain esters, lactones, ethers, and amides are preferably used. Since the electrochemical properties are synergistically improved over a wide temperature range, it is preferable to contain a chain ester, more preferably to contain a chain carbonate, and most preferably to contain both a cyclic carbonate and a chain carbonate. preferable.

The term "chain ester" is used as a concept including a chain carbonate and a chain carboxylic acid ester.

Cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 4-fluoro-1,3-dioxolane-2-one (FEC), trans or Sis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter, both are collectively referred to as "DFEC"), vinylene carbonate (VC), vinylethylene carbonate (VEC), and 4-ethynyl-1. , 3-Dioxolane-2-one (EEC), one or more, including ethylene carbonate, propylene carbonate, 4-fluoro-1,3-dioxolan-2-one, vinylene carbonate and 4-ethynyl. One or more selected from -1,3-dioxolane-2-one is more preferable.

Further, it is preferable to use at least one of the unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond or a cyclic carbonate having a fluorine atom because the electrochemical properties in a high temperature environment are further improved. It is more preferable to contain both a cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond and a cyclic carbonate having a fluorine atom. The cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond is more preferably VC, VEC or EEC, and the cyclic carbonate having a fluorine atom is further preferably FEC or DFEC.

The content of the cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond is preferably 0.07% by volume or more, more preferably 0.% by volume, based on the total volume of the non-aqueous solvent. It is 2% by volume or more, more preferably 0.7% by volume or more, and the upper limit thereof is preferably 7% by volume or less, more preferably 4% by volume or less, still more preferably 2.5% by volume or less. This is preferable because the electrochemical properties in a wider temperature range can be increased without impairing the Li ion permeability.

The content of the cyclic carbonate having a fluorine atom is preferably 0.07% by volume or more, more preferably 4% by volume or more, still more preferably 6% by volume or more, based on the total volume of the non-aqueous solvent. When the upper limit is preferably 35% by volume or less, more preferably 25% by volume or less, and further 15% by volume or less, the electrochemical characteristics in a wider temperature range can be improved without impairing the Li ion permeability. It is preferable because it can be done.

When the non-aqueous solvent contains both a cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond and a cyclic carbonate having a fluorine atom, carbon-with respect to the content of the cyclic carbonate having a fluorine atom. The content of the cyclic carbonate having an unsaturated bond such as a carbon double bond or a carbon-carbon triple bond is preferably 0.2% by volume or more, more preferably 3% by volume or more, still more preferably 7% by volume or more. When the upper limit is preferably 40% by volume or less, more preferably 30% by volume or less, and further 15% by volume or less, the electrochemical characteristics in a wider temperature range are improved without impairing the Li ion permeability. It is particularly preferable because it can be used.

Also, when the non-aqueous solvent contains both ethylene carbonate and a cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, electrochemistry of the coating formed on the electrode over a wide temperature range. The content of ethylene carbonate and cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond is preferable with respect to the total volume of the non-aqueous solvent. It is 3% by volume or more, more preferably 5% by volume or more, further preferably 7% by volume or more, and the upper limit thereof is preferably 45% by volume or less, more preferably 35% by volume or less, still more preferably 25% by volume. % Or less.

One type of these solvents may be used, and when two or more types are used in combination, the effect of improving the electrochemical properties in a high temperature environment is further improved, so that it is preferable to use three or more types in combination. It is particularly preferable to do so. Suitable combinations of these cyclic carbonates include EC and PC, EC and VC, PC and VC, VC and FEC, EC and FEC, PC and FEC, FEC and DFEC, EC and DFEC, PC and DFEC, VC and DFEC. , VEC and DFEC, VC and EEC, EC and EEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and VEC, EC and VC and EEC, EC and EEC and FEC, PC And VC and FEC, EC and VC and DFEC, PC and VC and DFEC, EC and PC and VC and FEC, or EC and PC and VC and DFEC are preferable. Of the above combinations, EC and VC, EC and FEC, PC and FEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and EEC, EC and EEC and FEC, PC and A combination of VC and FEC, or EC and PC and VC and FEC is more preferable.

Examples of the chain ester include one or more asymmetric chain carbonates selected from methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, and ethyl propyl carbonate. One or more symmetrical chain carbonates selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, and dibutyl carbonate, pivalic acid esters such as methyl pivalate, ethyl pivalate, and propyl pivalate. , One or more chain carboxylic acid esters selected from methyl propionate, ethyl propionate, propyl propionate, methyl acetate, and ethyl acetate (EA) are preferred.

Among the chain esters, a chain ester having a methyl group selected from dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, methyl propionate, methyl acetate and ethyl acetate (EA) is preferable. In particular, a chain carbonate having a methyl group is preferable.

Further, from the viewpoint of improving the electrochemical properties under high voltage, it is preferable to contain at least one chain ester in which at least one hydrogen atom is replaced with a fluorine atom.

Specific chain esters in which at least one hydrogen atom is substituted with a fluorine atom include 2,2-difluoroethyl acetate (DFEA), 2,2,2-trifluoroethyl acetate (TFEA), 2,2. -Difluoroethyl propionate, 2,2,2-trifluoroethyl propionate, methyl 2,2-difluoropropionate, methyl 2,2,2-trifluoropropionate, methyl (2,2-difluoroethyl) ) One or more selected from the group consisting of carbonate (MDFEC) and ethyl (2,2,2-tolyloethyl) carbonate (ETFEC) is preferably mentioned.
Above all, from the viewpoint of improving electrochemical properties in a high temperature environment, 2,2,2-trifluoroethyl acetate, 2,2-difluoroethyl acetate, 2,2,2-trifluoropropionate, methyl (2,2-) Difluoroethyl) carbonate or ethyl (2,2,2-triluoloethyl) carbonate is more preferred.

When chain carbonate is used, it is preferable to use two or more kinds. Further, it is more preferable that both the symmetric chain carbonate and the asymmetric chain carbonate are contained, and it is further preferable that the content of the symmetric chain carbonate is higher than that of the asymmetric chain carbonate.

The content of the chain ester is not particularly limited, but it is preferably used in the range of 60 to 90% by volume with respect to the total volume of the non-aqueous solvent. If the content is 60% by volume or more, the viscosity of the non-aqueous electrolyte solution does not become too high, and if it is 90% by volume or less, the electrical conductivity of the non-aqueous electrolyte solution decreases and the electrochemical characteristics in a wide temperature range Is less likely to decrease, so the above range is preferable.

The volume ratio of the symmetrical chain carbonate to the chain carbonate is preferably 51% by volume or more, more preferably 55% by volume or more. The upper limit is more preferably 95% by volume or less, and further preferably 85% by volume or less. It is particularly preferable that the symmetric chain carbonate contains dimethyl carbonate. Further, the asymmetric chain carbonate is more preferably having a methyl group, and methyl ethyl carbonate is particularly preferable. In the above case, the electrochemical characteristics in a wider temperature range are improved, which is preferable.

The ratio of the cyclic carbonate to the chain ester is preferably 10:90 to 45:55, preferably 15:85 to 40:60, from the viewpoint of improving the electrochemical properties at high temperature, and the cyclic carbonate: chain ester (volume ratio) is preferably 10:90 to 45:55. Is more preferable, and 20:80 to 35:65 is particularly preferable.

Other non-aqueous solvents include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and 1,4-dioxane, chains such as 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-dibutoxyethane. One or more selected from amides such as ether, dimethylformamide, sulfones such as sulfolane, and lactones such as γ-butyrolactone (GBL), γ-valerolactone, and α-angelica lactone are preferably mentioned.

The other non-aqueous solvents mentioned above are usually mixed and used in order to achieve appropriate physical characteristics. The combination is preferably a combination of a cyclic carbonate, a chain ester and a lactone, a combination of a cyclic carbonate, a chain ester and an ether, and the like, and a combination of a cyclic carbonate, a chain ester and a lactone is more preferable. Among the lactones, it is more preferable to use γ-butyrolactone (GBL).

The content of the other non-aqueous solvent is usually 1% or more, preferably 2% or more, and usually 40% or less, preferably 30% or less, more preferably 20%, based on the total volume of the non-aqueous solvent. It is as follows.

It is preferable to add other additives to the non-aqueous electrolyte solution for the purpose of improving the electrochemical properties in a wider temperature range.
Specific examples of other additives preferably include the following compounds (A) to (I).

(A) One or more nitriles selected from the group consisting of acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, pimeronitrile, suberonitrile, and sebaconitrile.

(B) Cyclohexylbenzene, fluorocyclohexylbenzene compounds (1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro-4-cyclohexylbenzene), tert-butylbenzene, tert-amylbenzene, 1 Aromatic compounds having a branched alkyl group such as −fluoro-4-tert-butylbenzene, biphenyl, terphenyl (o−, m−, p− form), diphenyl ether, fluorobenzene, difluorobenzene (o−, m). -, P-form), anisole, 2,4-difluoroanisole, partial hydride of terphenyl (1,2-dicyclohexylbenzene, 2-phenylbicyclohexyl, 1,2-diphenylcyclohexane, o-cyclohexylbiphenyl), etc. Aromatic compounds.

(C) Consists of methyl isocyanate, ethyl isocyanate, butyl isocyanate, phenylisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 1,4-phenylenediocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate. One or more isocyanate compounds selected from the group.

(D) 2-propynyl Methyl carbonate, 2-propynyl acetate, 2-propynyl formate, 2-propynyl methacrylate, 2-propynyl methanesulfonic acid, 2-propynyl vinylsulfonic acid, 2- (methanesulfonyloxy) propionic acid 2-propynyl Propinyl, di (2-propynyl) oxalate, methyl 2-propynyl oxalate, ethyl 2-propynyl oxalate, di (2-propynyl) glutarate, 2-butin-1,4-diyldimethanesulfonate, 2- One or more triple bond-containing compounds selected from the group consisting of butin-1,4-diyldiformate and 2,4-hexadiyne-1,6-diyldimethanesulfonate.

(E) 1,3-Propane sultone, 1,3-butane sultone, 2,4-butane sultone, 1,4-butane sultone, 1,3-propensultone, 2,2-dioxide-1,2-oxathiolan-4-yl Sultone such as acetate or 5,5-dimethyl-1,2-oxathiolane-4-one 2,2-dioxide, ethylene sulphite, hexahydrobenzo [1,3,2] dioxathiolane-2-oxide (1,2) -Cyclohexanediol cyclic sulphite), or cyclic sulphite such as 5-vinyl-hexahydro-1,3,2-benzodioxathiol-2-oxide, butane-2,3-diyldimethanesulfonate, butane. Sulfonic acid esters such as -1,4-diyldimethanesulfonate or methylenemethanedisulfonate, vinylsulfone compounds such as divinylsulfone, 1,2-bis (vinylsulfonyl) ethane, or bis (2-vinylsulfonylethyl) ether. One or more S = O group-containing compounds selected from the group consisting of.

(F) Cyclic acetal compounds such as 1,3-dioxolane, 1,3-dioxane, and 1,3,5-trioxane.

(G) trimethyl phosphate, tributyl phosphate, and trioctyl phosphate, tris phosphate (2,2,2-trifluoroethyl), bis (2,2,2-trifluoroethyl) methyl phosphate, bis phosphate (2,2,2-trifluoroethyl) ethyl, bis phosphate (2,2,2-trifluoroethyl) 2,2-difluoroethyl, bis phosphate (2,2,2-trifluoroethyl) 2, 2,3,3-Tetrafluoropropyl, bis phosphate (2,2-difluoroethyl) 2,2,2-trifluoroethyl, bis phosphate (2,2,3,3-tetrafluoropropyl) 2,2 , 2-Trifluoroethyl and Phosphate (2,2,2-Trifluoroethyl) (2,2,3,3-Tetrafluoropropyl) Methyl, Tris Phosphate (1,1,1,3,3,3) -Hexafluoropropan-2-yl), methyl methylenebisphosphonate, ethyl methylenebisphosphonate, methyl ethylenebisphosphonate, ethyl ethylenebisphosphonate, methyl butylenebisphosphonate, ethyl butylenebisphosphonate, methyl 2- (dimethylphosphoryl) acetate, ethyl 2- (Dimethylphosphoryl) acetate, methyl 2- (diethylphosphoryl) acetate, ethyl 2- (diethylphosphoryl) acetate, 2-propynyl 2- (dimethylphosphoryl) acetate, 2-propynyl 2- (diethylphosphoryl) acetate, methyl 2 -(Dimethoxyphosphoryl) acetate, ethyl 2- (dimethoxyphosphoryl) acetate, methyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) acetate, 2-propynyl 2- (dimethoxyphosphoryl) acetate, 2-propynyl One or more phosphorus-containing compounds selected from the group consisting of 2- (diethoxyphosphoryl) acetate, methyl pyrophosphate, and ethyl pyrophosphate.

(H) Chain carboxylic acid anhydrides such as acetic anhydride and propionic anhydride, succinic anhydride, maleic anhydride, 3-allyl succinic anhydride, glutaric anhydride, itaconic anhydride, or 3-sulfo-propionic anhydride. Cyclic acid anhydride such as a thing.

(I) Cyclic phosphazene compounds such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, or ethoxyheptafluorocyclotetraphosphazene.

Among the above, it is preferable to include at least one selected from the group consisting of (A) nitrile, (B) aromatic compound, and (C) isocyanate compound because the electrochemical properties in a wider temperature range are improved.

Among the nitriles (A), one or more selected from the group consisting of succinonitrile, glutaronitrile, adiponitrile, and pimeronitrile are more preferable.

(B) Among aromatic compounds, one or two selected from biphenyl, terphenyl (o-, m-, p-form), fluorobenzene, cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene. The above is more preferable, and one or more selected from the group consisting of biphenyl, o-terphenyl, fluorobenzene, cyclohexylbenzene, and tert-amylbenzene is particularly preferable.

Among the isocyanate compounds (C), one or more selected from hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate are more preferable.

The content of the compounds (A) to (C) is preferably 0.01 to 7% by mass in the non-aqueous electrolytic solution. In this range, the coating is sufficiently formed without becoming too thick, and the electrochemical properties in a wider temperature range are enhanced. The content is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and the upper limit thereof is more preferably 5% by mass or less, further preferably 3% by mass or less in the non-aqueous electrolytic solution. ..

Further, a cyclic or chain S = O group-containing compound selected from (D) triple bond-containing compound, (E) sulton, cyclic sulfite, sulfonic acid ester, and vinyl sulfone, (F) cyclic acetal compound, (G). It is preferable to include a phosphorus-containing compound, (H) cyclic acid anhydride, and (I) cyclic phosphazene compound because the electrochemical characteristics in a wider temperature range are improved.

(D) Examples of the triple bond-containing compound include 2-propynyl methyl carbonate, 2-propynyl methacrylate, 2-propynyl methanesulfonic acid, 2-propynyl vinylsulfonic acid, 2-propynyl 2- (methanesulfonyloxy) propionyl, and dipynyl. One or more selected from (2-propynyl) oxalate, methyl 2-propynyl oxalate, ethyl 2-propynyl oxalate, and 2-butyne-1,4-diyldimethanesulfonate, preferably methanesulfonic acid 2-propynyl, One selected from the group consisting of vinylsulfonic acid 2-propynyl, 2- (methanesulfonyloxy) propionic acid 2-propynyl, di (2-propynyl) oxalate, and 2-butin-1,4-diyldimethanesulfonate. Two or more are more preferable.

(E) A cyclic or chain S = O group-containing compound selected from the group consisting of sultone, cyclic sulfite, sulfonic acid ester, and vinyl sulfone (provided that the compound contains a triple bond and is represented by any of the above general formulas. It is preferable to use (does not include the specific compound to be used).

Examples of the cyclic S = O group-containing compound include 1,3-propane sultone, 1,3-butane sultone, 1,4-butane sultone, 2,4-butane sultone, 1,3-propensultone, and 2,2-dioxide-. 1,2-oxathiolan-4-yl acetate, 5,5-dimethyl-1,2-oxathiolan-4-one 2,2-dioxide, methylene methanedisulfonate, ethylene sulphite, and 4- (methylsulfonylmethyl)- One or more selected from the group consisting of 1,3,2-dioxathiolane 2-oxide is preferably used.

Examples of the chain S = O group-containing compound include butane-2,3-diyldimethanesulfonate, butane-1,4-diyldimethanesulfonate, dimethylmethanedisulfonate, pentafluorophenylmethanesulfonate, and divinylsulfone. And one or more selected from the group consisting of bis (2-vinylsulfonylethyl) ether are preferably mentioned.

Among the cyclic or chain S = O group-containing compounds, 1,3-propanesulfone, 1,4-butanesulfone, 2,4-butanesulfone, 2,2-dioxide-1,2-oxathiolan-4-yl acetate. , Ethylene sulfate, pentafluorophenyl methanesulfonate, and one or more selected from the group consisting of divinyl sulfone are more preferable.

As the cyclic acetal compound (F), 1,3-dioxolane or 1,3-dioxane is preferable, and 1,3-dioxane is more preferable.

Examples of the phosphorus-containing compound (G) include tris phosphate (2,2,2-trifluoroethyl), tris phosphate (1,1,1,3,3,3-hexafluoropropan-2-yl), and methyl. 2- (Dimethylphosphoryl) acetate, ethyl 2- (dimethylphosphoryl) acetate, methyl 2- (diethylphosphoryl) acetate, ethyl 2- (diethylphosphoryl) acetate, 2-propynyl 2- (dimethylphosphoryl) acetate, 2-propynyl 2 -(Diethylphosphoryl) acetate, methyl 2- (dimethoxyphosphoryl) acetate, ethyl 2- (dimethoxyphosphoryl) acetate, methyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) acetate, 2-propynyl 2- (Dimethoxyphosphoryl) acetate or 2-propynyl 2- (diethoxyphosphoryl) acetate is preferable, tris phosphate (2,2,2-trifluoroethyl), tris phosphate (1,1,1,3,3,3). 3-Hexafluoropropan-2-yl), ethyl 2- (diethylphosphoryl) acetate, 2-propynyl 2- (dimethylphosphoryl) acetate, 2-propynyl 2- (diethylphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) Acetates, 2-propynyl 2- (dimethoxyphosphoryl) acetate, or 2-propynyl 2- (diethoxyphosphoryl) acetate are more preferred.

As the cyclic acid anhydride, succinic anhydride, maleic anhydride, or 3-allyl succinic anhydride is preferable, and succinic anhydride or 3-allyl succinic anhydride is more preferable.

(I) As the cyclic phosphazene compound, a cyclic phosphazene compound such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, or phenoxypentafluorocyclotriphosphazene is preferable, and methoxypentafluorocyclotriphosphazene or ethoxypentafluorocyclocyclo Triphosphazene is more preferred.

The content of the compounds (D) to (I) is preferably 0.001 to 5% by mass in the non-aqueous electrolytic solution. In this range, the coating is sufficiently formed without becoming too thick, and the electrochemical properties in a wider temperature range are enhanced. The content is more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, and the upper limit thereof is more preferably 3% by mass or less, further preferably 2% by mass or less in the non-aqueous electrolytic solution. ..

Further, for the purpose of improving the electrochemical properties in a wider temperature range, a lithium salt having a oxalic acid skeleton, a lithium salt having a phosphoric acid skeleton, and a lithium salt having an S = O group are further contained in a non-aqueous electrolytic solution. It is preferable to contain one or more lithium salts selected from the above.
Specific examples of lithium salts include lithium bis (oxalate) borate [LiBOB], lithium difluoro (oxalat) borate [LiDFOB], lithium tetrafluoro (oxalat) phosphate [LiTFOP], and lithium difluorobis (oxalate) phosphate [LiDFOP]. Lithium salt having at least one oxalate skeleton selected from, lithium salt having _{a phosphoric acid skeleton such as LiPO 2} F ₂ and Li ₂ PO ₃ F, lithium trifluoro ((methanesulfonyl) oxy) borate [LiTFMSB], lithium Selected from pentafluoro ((methanesulfonyl) oxy) phosphate [LiPFMSP], lithium methyl sulfate [LMS], lithium ethyl sulfate [LES], lithium 2,2,2-trifluoroethyl sulfate [LFES], and FSO ₃ Li. Lithium salts having one or more S = O groups are preferably mentioned and include lithium salts selected from _{LiBOB, LiDFOB, LiTFOP, LiDFOP, LiPO 2} F ₂ , LiTFMSB, LMS, LES, LFES, and FSO _{3 Li.} Is more preferable.

The ratio of the lithium salt in the non-aqueous solvent is preferably 0.001 M or more and 0.5 M or less. Within this range, the effect of improving the electrochemical characteristics in a wide temperature range is further exhibited. It is preferably 0.01 M or more, more preferably 0.03 M or more, and particularly preferably 0.04 M or more. The upper limit is more preferably 0.4 M or less, and particularly preferably 0.2 M or less. (However, M indicates mol / L.)

(Electrolyte salt)
Preferred examples of the electrolyte salt used in the present invention include the following lithium salts.
Lithium salts include inorganic lithium salts such _{as LiPF 6} , LiBF ₄ , and LiClO _{4 , LiN (SO 2} F) ₂ [LiFSI], LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiCF ₃ SO ₃ , LiC (SO ₂ CF ₃ ) ₃ , LiPF ₄ (CF ₃ ) ₂ , LiPF ₃ (C ₂ F ₅ ) ₃ , LiPF ₃ (CF ₃ ) ₃ , LiPF ₃ (iso-C ₃ F ₇ ) ₃ , Lithium salt containing a chain-like alkyl fluoride group such as _{LiPF 5} (iso-C ₃ F _{7 ), (CF 2} ) ₂ (SO ₂ ) ₂ NLi, (CF ₂ ) ₃ (SO ₂ ) ₂ Lithium salts having a cyclic fluorinated alkylene chain such as NLi are preferably mentioned, and at least one lithium salt selected from these is preferably mentioned, and one or more of these are mixed. Can be used.
Among these, one or more selected from _{LiPF 6} , LiBF ₄ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , and LiN (SO ₂ F) _{2 [LiFSI].} Is preferable, and it is most preferable to use _{LiPF 6.} The concentration of the electrolyte salt is usually preferably 0.3 M or more, more preferably 0.7 M or more, still more preferably 1.1 M or more, relative to the above-mentioned non-aqueous solvent. The upper limit thereof is preferably 2.5 M or less, more preferably 2.0 M or less, and even more preferably 1.6 M or less.
In addition, a suitable combination of these electrolyte salts includes _{LiPF 6} , and at least one lithium selected from _{LiBF 4} , LiN (SO ₂ CF ₃ ) ₂ , and LiN (SO ₂ F) _{2 [LiFSI].} It is preferable that the salt is contained in the non-aqueous electrolyte solution, and when _{the ratio of the lithium salt other than LiPF 6 in the} non-aqueous solvent is 0.001 M or more, the electrochemical properties are improved in a wide temperature range. The effect is easily exhibited, and when it is 1.0 M or less, there is little concern that the effect of improving the electrochemical characteristics in a wide temperature range is reduced, which is preferable. It is preferably 0.01 M or more, particularly preferably 0.03 M or more, and most preferably 0.04 M or more. The upper limit is preferably 0.8 M or less, more preferably 0.6 M or less, and particularly preferably 0.4 M or less.

[Manufacturing of non-aqueous electrolyte solution]
The non-aqueous electrolyte solution of the present invention is, for example, mixed with the non-aqueous solvent, and is represented by the general formula (I) with respect to the electrolyte salt and the non-aqueous electrolyte solution (2-oxo-1). , 3-Dioxolan-4-yl) It can be obtained by adding an oxy derivative compound.
At this time, it is preferable that the compound to be added to the non-aqueous solvent and the non-aqueous electrolytic solution to be used is purified in advance within a range that does not significantly reduce the productivity, and has as few impurities as possible.

The non-aqueous electrolyte solution of the present invention can be used in the following first to fourth power storage devices, and as the non-aqueous electrolyte solution, not only a liquid one but also a gelled one can be used. Further, the non-aqueous electrolyte solution of the present invention can also be used for solid polymer electrolytes. Of these, it is preferably used for a first power storage device (that is, for a lithium battery) or a fourth power storage device (that is, for a lithium ion capacitor) that uses a lithium salt as an electrolyte salt, and is preferably used for a lithium battery. It is more preferable, and it is further preferable to use it for a lithium secondary battery.

[First power storage device (lithium battery)]
In the present specification, the lithium battery is a general term for a lithium primary battery and a lithium secondary battery. Further, in the present specification, the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
The lithium battery, which is the first power storage device of the present invention, comprises the positive electrode, the negative electrode, and the non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent. Constituent members such as positive electrodes and negative electrodes other than the non-aqueous electrolytic solution can be used without particular limitation.
For example, as the positive electrode active material for a lithium secondary battery, a composite metal oxide containing one or more selected from the group consisting of cobalt, manganese, and nickel is used. These positive electrode active materials can be used alone or in combination of two or more.
Examples of such a lithium composite metal oxide include LiCoO ₂ , LiCo _1-x M _x O ₂ (where M is Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, and One or more elements selected from Cu, 0.001 ≤ x ≤ 0.05), LiMn ₂ O ₄ , LiNiO ₂ , LiCo _1-x Ni _x O ₂ (0.01 <x <1), LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _0.3 Co _0.2 Mn _0.3 O ₂ , LiNi _0.8 Mn _0.1 Co _0.1 O ₂ , LiNi _0.8 Co _0.15 Al _0.05 O ₂ , Li ₂ MnO ₃ and LiMO ₂ (M is a transition metal such as Co, Ni, Mn, Fe), and LiNi _1/2 Mn _3/2. one or more selected from the group consisting of O ₄ is preferably mentioned, two or more is more preferable. Further, LiCoO ₂ and LiMn ₂ O ₄ , LiCoO ₂ and LiNiO ₂ , LiMn ₂ O ₄ and LiNiO ₂ may be used in combination.

When a lithium composite metal oxide operating at a high charging voltage is used, the electrochemical characteristics tend to deteriorate in a high temperature environment due to the reaction with the electrolytic solution during charging. However, in the lithium secondary battery according to the present invention, these electrochemical properties are likely to deteriorate. Deterioration of characteristics can be suppressed.
In particular, in the case of a positive electrode active material containing Ni, the catalytic action of Ni causes decomposition of the non-aqueous solvent on the surface of the positive electrode, and the resistance of the battery tends to increase. In particular, the electrochemical characteristics tend to deteriorate in a high temperature environment, but the lithium secondary battery according to the present invention is preferable because the deterioration of these electrochemical characteristics can be suppressed. In particular, when the ratio of the atomic concentration of Ni to the atomic concentration of all transition metal elements in the positive electrode active material exceeds 10 atomic%, the above effect becomes remarkable, and 20 atomic% or more is more preferable. , 30 atomic% or more is particularly preferable. Specifically, LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _0.3 Co _0.2 Mn _0.3 O ₂ , LiNi _0.8 Mn _0.1 Co _0. Preferred examples thereof include ₁ O ₂ , LiNi _0.8 Co _0.15 Al _0.05 O _2.

Further, as the positive electrode active material, a lithium-containing olivine-type phosphate can also be used. In particular, a lithium-containing olivine-type phosphate containing one or more selected from iron, cobalt, nickel and manganese is preferable. Specific examples thereof include one or more selected from _{LiFePO 4} , LiCoPO ₄ , LiNiPO ₄ , and LiMnPO _4.
Some of these lithium-containing olivine-type phosphates may be replaced with other elements, and some of iron, cobalt, nickel and manganese may be replaced with Co, Mn, Ni, Mg, Al, B, Ti, V and Nb. , Cu, Zn, Mo, Ca, Sr, W, and Zr can be substituted with one or more elements selected from, or coated with a compound or carbon material containing these other elements. Of these, LiFePO ₄ or LiMnPO ₄ is preferred.
Further, the lithium-containing olivine-type phosphate can also be used, for example, by mixing with the above-mentioned positive electrode active material.

Further, as the positive electrode for the lithium primary battery, CuO, Cu ₂ O, Ag ₂ O, Ag ₂ CrO ₄ , CuS, CuSO ₄ , TiO ₂ , TiS ₂ , SiO ₂ , SnO, V ₂ O ₅ , V ₆ O ₁₂ , VO _x , Nb ₂ O ₅ , Bi ₂ O ₃ , Bi ₂ Pb ₂ O ₅ , Sb ₂ O ₃ , CrO ₃ , Cr ₂ O ₃ , MoO ₃ , WO ₃ , SeO ₂ , MnO ₂ , Mn ₂ O ₃ , Fe ₂ O ₃ , FeO, Fe ₃ O ₄ , Ni ₂ O ₃ , NiO, CoO ₃ , CoO, etc., oxides or chalcogen compounds of one or more metal elements, SO ₂ , SOCl _2, etc. Examples thereof include compounds, fluorocarbon (fluorinated graphite) represented by _{the general formula (CF x} ) _{n, and the like.} Among these, MnO ₂ , V ₂ O ₅ , fluorographite and the like are preferable.

The conductive agent for the positive electrode is not particularly limited as long as it is an electron conductive material that does not cause a chemical change. Examples thereof include natural graphite (scaly graphite and the like), graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, carbon black such as thermal black and the like. Further, graphite and carbon black may be appropriately mixed and used. The amount of the conductive agent added to the positive electrode mixture is preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.

For the positive electrode, the positive electrode active material is made of a conductive agent such as acetylene black or carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a styrene / butadiene copolymer (SBR), or acrylonitrile and butadiene. Mix with a binder such as copolymer (NBR), carboxymethyl cellulose (CMC), ethylene propylene dienter polymer, etc., add a high boiling point solvent such as 1-methyl-2-pyrrolidone, and knead to make a positive electrode mixture. After that, this positive electrode mixture is applied to an aluminum foil of a current collector, a lath plate made of stainless steel, etc., dried and pressure-molded, and then at a temperature of about 50 ° C to 250 ° C under vacuum for about 2 hours. It can be produced by heat treatment.
The density of the part except the collector of the positive electrode is usually at 1.5 g / cm ³ or more, for further increasing the capacity of the battery, it is preferably 2 g / cm ³ or more, more preferably, 3 g / cm ³ The above is more preferably 3.6 g / cm ³ or more. The upper limit thereof ^{is preferably 4 g / cm 3} or less.

As the negative electrode active material for lithium secondary batteries, lithium metal, lithium alloy, and a carbon material capable of storing and releasing lithium [graphitized carbon and (002) plane spacing of 0.37 nm or more Graphitized carbon, graphite with (002) plane spacing of 0.34 nm or less], tin (elemental substance), tin compound, silicon (elemental substance), silicon compound, or titanium acid such as _{Li 4} Ti ₅ O ₁₂ Lithium compounds and the like can be used alone or in combination of two or more.
Among these, it is more preferable to use a highly crystalline carbon material such as artificial graphite or natural graphite in terms of the ability to occlude and release lithium ions, and the interplanar spacing (d ₀₀₂ ) of the lattice plane (002) is 0. It is more preferable to use a carbon material having a graphite-type crystal structure of 340 nm (nanometer) or less, particularly 0.335 to 0.337 nm.
In particular, artificial graphite particles having a massive structure in which a plurality of flat graphite fine particles are assembled or bonded in a non-parallel manner to each other, and mechanical actions such as compressive force, frictional force, and shearing force are repeatedly applied to form scaly natural graphite spherical. It is preferable to use the treated particles.
The peak intensity I (110) of the (110) plane of the graphite crystal obtained from the X-ray diffraction measurement of the negative electrode sheet when the density of the portion of the negative electrode excluding the current collector ^{is pressure-molded to a density of 1.5 g / cm 3 or more.} ) And the peak intensity I (004) of the plane (004) when I (110) / I (004) is 0.01 or more, the electrochemical characteristics in a wider temperature range are improved, which is preferable, 0.05 or more. It is more preferable that it is 0.1 or more, and it is further preferable that it is 0.1 or more. Further, since excessive treatment may reduce the crystallinity and the discharge capacity of the battery, the upper limit of the peak intensity ratio I (110) / I (004) is preferably 0.5 or less, and 0. 3 or less is more preferable.
Further, it is preferable that the highly crystalline carbon material (core material) is coated with a carbon material having a lower crystallinity than the core material because the electrochemical properties in a wide temperature range are further improved. The crystallinity of the coated carbon material can be confirmed by TEM.
When a highly crystalline carbon material is used, it reacts with a non-aqueous electrolytic solution during charging and tends to reduce the electrochemical properties at low temperature or high temperature due to an increase in interfacial resistance. Good electrochemical properties over a wide temperature range.

Examples of the metal compound capable of occluding and releasing lithium as a negative electrode active material include Si, Ge, Sn, Pb, P, Sb, Bi, Al, Ga, In, Ti, Mn, Fe, Co, Ni and Cu. , Zn, Ag, Mg, Sr, or a compound containing at least one metal element such as Ba. These metal compounds may be used in any form such as elemental substances, alloys, oxides, nitrides, sulfides, borides, alloys with lithium, etc., but any of elemental substances, alloys, oxides, alloys with lithium, etc. It is preferable because the capacity can be increased. Among them, those containing at least one element selected from the group consisting of Si, Ge and Sn are preferable, and those containing at least one element selected from Si and Sn are particularly preferable because the capacity of the battery can be increased.

The negative electrode is kneaded with a conductive agent, a binder, and a high boiling point solvent similar to those for producing the positive electrode to obtain a negative electrode mixture, and then this negative electrode mixture is applied to a copper foil or the like of a current collector. After drying and pressure molding, it can be produced by heat treatment at a temperature of about 50 ° C. to 250 ° C. for about 2 hours under vacuum.
The density of the portion of the negative electrode excluding the current collector is usually 1.1 g / cm ^{3 or more, and is preferably 1.5 g / cm 3} or more, more preferably 1.7 g in order to further increase the capacity of the battery. / Cm ³ or more. The upper limit thereof ^{is preferably 2 g / cm 3} or less.

Moreover, as a negative electrode active material for a lithium primary battery, a lithium metal or a lithium alloy can be mentioned.

The structure of the lithium battery is not particularly limited, and a coin-type battery having a single-layer or multi-layer separator, a cylindrical battery, a square battery, a laminated battery, or the like can be applied.
The battery separator is not particularly limited, but a monolayer or laminated microporous film of polyolefin such as polypropylene or polyethylene, a woven fabric, a non-woven fabric, or the like can be used.

The lithium secondary battery in the present invention has excellent electrochemical characteristics in a wide temperature range even when the charge termination voltage is 4.2 V or more, particularly 4.3 V or more, and further, the characteristics are good even when the charge termination voltage is 4.4 V or more. is there. The discharge end voltage can usually be 2.8 V or higher, further 2.5 V or higher, but the lithium secondary battery in the present invention can be 2.0 V or higher. The current value is not particularly limited, but is usually used in the range of 0.1 to 30C. Further, the lithium battery in the present invention can be charged and discharged at −40 to 100 ° C., preferably −10 to 80 ° C.

In the present invention, as a countermeasure against an increase in the internal pressure of the lithium battery, a method of providing a safety valve on the battery lid or making a notch in a member such as a battery can or a gasket can also be adopted. Further, as a safety measure for preventing overcharging, a current cutoff mechanism that senses the internal pressure of the battery and cuts off the current can be provided on the battery lid.

[Second power storage device (electric double layer capacitor)]
The second power storage device is a power storage device that stores energy by utilizing the electric double layer capacity at the interface between the electrolytic solution and the electrode. An example of the present invention is an electric double layer capacitor. The most typical electrode active material used in this power storage device is activated carbon. The double layer capacity increases roughly in proportion to the surface area.

[Third power storage device]
The third storage device is a storage device that stores energy by utilizing the doping / dedoping reaction of the electrodes. Examples of the electrode active material used in this power storage device include metal oxides such as ruthenium oxide, iridium oxide, tungsten oxide, molybdenum oxide and copper oxide, and π-conjugated polymers such as polyacene and polythiophene derivatives. Capacitors using these electrode active materials can store energy associated with the doping / dedoping reaction of the electrodes.

[Fourth power storage device (lithium ion capacitor)]
The fourth power storage device is a power storage device that stores energy by utilizing the intercalation of lithium ions with a carbon material such as graphite, which is a negative electrode. It is called a lithium ion capacitor (LIC). Examples of the positive electrode include those using an electric double layer between the activated carbon electrode and the electrolytic solution, those using the doping / dedoping reaction of the π-conjugated polymer electrode, and the like. The electrolytic solution contains at least a lithium salt such as _{LiPF 6.}

The (2-oxo-1,3-dioxolane-4-yl) oxy derivative compound which is a novel compound of the present invention is represented by the following general formula (II).

（式中、Ｒ^８は、水素原子、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、−ＯＣ（＝Ｏ）−Ｒ^９、−ＯＳ（＝Ｏ）_２−Ｒ^５、又は−ＯＰ（＝Ｏ）（−Ｒ^６）−Ｒ^７を示す。Ｒ^２及びＲ^３は、水素原子、ハロゲン原子、又は少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数１〜６のアルキル基を示し、ｎは１〜３の整数を示す。ｎが１の場合、Ｌ^２は−Ｃ（＝Ｏ）−Ｒ^９、−Ｓ（＝Ｏ）_２−Ｒ^５、又は−Ｐ（＝Ｏ）（−Ｒ^６）−Ｒ^７を示し、ｎが２の場合、Ｌ^２は−Ｃ（＝Ｏ）Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）_２−、又は−Ｐ（＝Ｏ）（−Ｒ^６）−を示し、ｎが３の場合、Ｌ^２は−Ｐ（＝Ｏ）（−）_２を示す。Ｒ^９は、少なくとも１つの水素原子がハロゲン原子で置換された炭素数１〜６のハロアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、又は少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数２〜６のアルコキシカルボニル基を示す。Ｒ^５は、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数７〜１３のアラルキル基、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリール基、又は少なくとも１つの水素原子がハロゲン原子で置換されていてもよい炭素数１〜６のアルコキシ基を示す。また、Ｒ^６及びＲ^７は、それぞれ独立して、ハロゲン原子、少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数１〜６のアルコキシ基、又は少なくとも１つの水素原子がハロゲン原子で置換されてもよい炭素数６〜１２のアリールオキシ基を示す。）

(In the formula, R ⁸ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, and a carbon number of carbon atoms. An alkenyl group of 2 to 6, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and at least one hydrogen atom being substituted with a halogen atom. An aryl group having 6 to 12 carbon atoms, which may be formed,: -OC (= O) -R ⁹ , -OS (= O) _2- R ⁵ , or -OP (= O) ( ^{-R 6} ) -R ⁷ . R ² and R ³ represent alkyl groups having 1 to 6 carbon atoms in which a hydrogen atom, a halogen atom, or at least one hydrogen atom may be substituted with a halogen atom, and n represents an integer of 1 to 3. When n is 1, L ² indicates -C (= O) -R ⁹ , -S (= O) _2- R ⁵ , or -P (= O) ( ^{-R 6} ) -R ⁷ , and n When is 2, L ² indicates −C (= O) C (= O) −, −S (= O) ₂₋ , or −P (= O) (−R ⁶ ) −, and n is 3. In the case, L ² indicates −P (= O) (−) _2. R ⁹ is a haloalkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is replaced with a halogen atom, and a cyclo having 3 to 6 carbon atoms. An alkyl group, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, and at least one hydrogen atom may be substituted with a halogen atom. An aryl group having 6 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms in which at least one hydrogen atom may be substituted with ^{a halogen atom. R 5} is a halogen atom, at least one hydrogen atom. An alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and at least one hydrogen. An aralkyl group having 7 to 13 carbon atoms in which the atom may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms in which at least one hydrogen atom may be substituted with a halogen atom, or at least one hydrogen atom. It represents an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. Further, R ⁶ and R ⁷ are independently each of a halogen atom, even if at least one hydrogen atom is substituted with a halogen atom. A good alkoxy group with 1 to 6 carbon atoms, or at least 1 It shows an aryloxy group having 6 to 12 carbon atoms in which one hydrogen atom may be substituted with a halogen atom. )

In formula (II), the same meaning as ^{R 2, R 3, R 5} , R 6, and ^{R 7} in the substituent ^{R 2, R 3, R 5} , R 6, and ^{R 7} of the general formula (I) ..

Wherein, specific examples of R ^8, a hydrogen atom, a fluorine atom, a chlorine atom or a halogen atom such as a bromine atom, a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group or, n- Linear alkyl group such as hexyl group, iso-propyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, tert-butyl group, or branched alkyl group such as tert-amyl group, fluoro Methyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3 , 3-Difluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, or 2,2,3,3,3-pentafluoropropyl group, etc. Cycloalkyl group such as alkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, or cycloheptyl group, vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, 2-butene -1-yl group, 3-butene-1-yl group, 4-penten-1-yl group, 5-hexene-1-yl group, 1-propen-2-yl group, 1-buten-2-yl group Or an alkenyl group such as 2-methyl-2-propen-1-yl group, ethynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 4-heptynyl group, 1-methyl-2-propynyl group. , 1,1-dimethyl-2-propynyl group, 1-methyl-3-butynyl group, or alkynyl group such as 1-methyl-4-heptynyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl Group, 4-fluorobenzyl group, 4-chlorobenzyl group, 1-phenylethane-1-yl group, 2-phenylethane-1-yl group, or aralkyl group such as 3-phenylpropan-1-yl group, phenyl Group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-tert-butylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-trifluoro Methylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenyl group, 2,6-difluorophenyl Methyl group, 3,5-difluoro Phenyl group, 2,4,6-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, or aryl group such as perfluorophenyl, fluorosulfonyloxy group, methanesulfonyloxy group, vinylsulfonyloxy group , Difluorophosphoryl group, dimethoxyphosphoryl group, diethoxyphosphoryl group and the like are preferably mentioned, and among them, hydrogen atom, fluorine atom, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and the like. n-hexyl group, iso-propyl group, sec-butyl group, 2-pentyl group, tert-butyl group, tert-amyl group, trifluoromethyl group, 2-fluoroethyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group , Vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, 1-propen-2-yl group, ethynyl group, 2-propynyl group, 2-butynyl group, benzyl group, 4-methyl A benzyl group, a phenyl group, a 4-methylphenyl group, a fluorosulfonyloxy group, a methanesulfonyloxy group, a vinylsulfonyloxy group, a difluorophosphoryl group, a dimethoxyphosphoryl group, or a diethoxyphosphoryl group is preferable, and a hydrogen atom, a fluorine atom, or a methyl group is preferable. Group, ethyl group, n-propyl group, iso-propyl group, tert-butyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, vinyl group, 1-propen-1-yl group, 1-propen-2- Il group, ethynyl group, 2-propynyl group, phenyl group, 4-methylphenyl group, fluorosulfonyloxy group, methanesulfonyloxy group, vinylsulfonyloxy group, difluorophosphoryl group, dimethoxyphosphoryl group, or diethoxyphosphoryl group. preferable.

The R ⁹ is a fluoromethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 2,2,2-trifluoroethyl group, a 3-fluoropropyl group, or a 3-chloropropyl group. Group, alkyl halides such as 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, or 2,2,3,3,3-pentafluoropropyl group, cyclopropyl Cycloalkyl group such as group, cyclobutyl group, cyclopentyl group, cyclohexyl group, or cycloheptyl group, ethynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 4-heptinyl group, 1-methyl-2- Alkinyl group such as propynyl group, 1,1-dimethyl-2-propynyl group, 1-methyl-3-butynyl group, or 1-methyl-4-pentynyl group, benzyl group, 4-methylbenzyl group, 1-phenylethane Aralkyl group such as -1-yl group, 2-phenylethane-1-yl group, or 3-phenylpropane-1-yl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl Group, 4-tert-butylphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl Group, 4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluoro Phenyl group, 2,3,5,6-tetrafluorophenyl group, aryl group such as perfluorophenyl, alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group are preferably mentioned, and among them, fluoromethyl group and tri Fluoromethyl group, 2-fluoroethyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, ethynyl group, 2-propynyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-Methylphenyl group, 4-fluorophenyl group, 4-trifluoromethylphenyl group, methoxycarbonyl group, or ethoxycarbonyl group is preferable, and trifluoromethyl group, cyclopropyl group, cyclohexyl group, ethynyl group, phenyl group, 4 -Fluorophenyl group, 4-trifluo A lophenyl group, a methoxycarbonyl group, or an ethoxycarbonyl group is more preferable.

The specific compound represented by the general formula (II) is the same as the description and preferred description of the specific compound of the general formula (I) except for the compound having the structural formula of A1 to A3, A7 to A8, or A20. Is.

Hereinafter, examples of an electrolytic solution using the compound of the present invention will be shown, but the present invention is not limited to these examples.

Synthesis example [Synthesis of 2-oxo-1,3-dioxolane-4-yl acetate (structural formula A1)]
To a solution of 2.50 g (20.4 mmol) of 4-chloro-1,3-dixolan-2-one in 27 ml of acetic acid, 2.10 g (21.4 mmol) of potassium acetate was added, and the mixture was heated under reflux under a nitrogen stream for 15 hours. The mixture was cooled to room temperature, filtered, washed with diethyl ether, and the filtrate was concentrated under reduced pressure. Diethyl ether was added to the residue, the mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 1.19 g (yield 40%) of the desired 2-oxo-1,3-dioxolan-4-yl acetate as an oil. The structure of the obtained 2-oxo-1,3-dioxolane-4-yl acetate was confirmed by measuring the ^{1 H-NMR spectrum.} The results are shown below.
^{1 1} H-NMR (400MHz, CDCl ₃ ) δ = 6.70 (dd, 1H, J = 5.7, 2.1Hz), 4.65 (dd, 1H, J = 10.1, 5.7Hz), 4.43 (dd, 1H, J = 10.1, 2.1Hz), 2.18 (s, 3H)

[Synthesis of bis (2-oxo-1,3-dioxolane-4-yl) oxalate (structural formula B1)]
The target bis (2-oxo-1,3-dioxolane-4-yl) was obtained as a white solid by the same method as described above. The structure of the obtained bis (2-oxo-1,3-dioxolane-4-yl) oxalate was confirmed by measuring the ^{1 H-NMR spectrum.} The results are shown below.
^{1 1} H-NMR (400MHz, DMSO-d6) δ = 6.79-6.75 (m, 2H), 4.85-4.79 (m, 2H), 4.66 (dd, 2H, J = 10.3, 1.8Hz)

[Synthesis of 2-oxo-1,3-dioxolane-4-ylmethanesulfonate (structural formula C2)]
Suspension of 6.09 g (30.0 mmol) of silver methanesulfonate in 10 ml of dichloromethane, add 3.06 g (25.0 mmol) of 4-chloro-1,3-disolan-2-one with stirring, and add a nitrogen stream. The mixture was heated under reflux for 6.5 hours. It was cooled to room temperature and silver chloride produced by filtration was removed. The filtrate is concentrated under reduced pressure, diethyl ether is added to the residue, and the mixture is filtered to obtain 2.00 g (yield 44%) of the desired 2-oxo-1,3-dioxolan-4-yl methanesulfonate as a white solid. It was. The structure of the obtained 2-oxo-1,3-dioxolane-4-ylmethanesulfonate was confirmed by measuring the ^{1 H-NMR spectrum.} The results are shown below.
^{1 1} H-NMR (400MHz, CDCl ₃ ) δ = 6.52 (dd, 1H, J = 5.7, 1.9Hz), 4.71 (dd, 1H, J = 10.5, 5.7Hz), 4.55 (dd, 1H, J = 10.5, 1.9Hz), 3.33 (s, 3H)

[Synthesis of 2-oxo-1,3-dioxolane-4-ylethenesulfonate (structural formula C9)]
By the same method as above, the desired 2-oxo-1,3-dioxolane-4-ylethenesulfonate was obtained as a white solid. The structure of the obtained 2-oxo-1,3-dioxolane-4-ylethanesulfonate was confirmed by measuring the ^{1 H-NMR spectrum.} The results are shown below.
^{1 1} H-NMR (400MHz, CDCl ₃ ) δ = 6.69 (dd, 1H, J = 16.5, 9.7Hz), 6.54 (dd, 1H, J = 16.5, 0.8Hz), 6.47 (dd, 1H, J = 5.6, 1.8Hz), 6.27 (dd, 1H, J = 9.7, 0.8Hz), 4.69 (dd, 1H, J = 10.5, 5.6Hz), 4.55 (dd, 1H, J = 10.5, 1.8Hz)

Examples 1-22, Comparative Examples 1-2
[Manufacturing of lithium-ion secondary battery]
LiNi _0.33 Mn _0.33 Co _0.34 O ₂ ; 94% by mass, acetylene black (conductive agent); 3% by mass is mixed, and polyvinylidene fluoride (binding agent); 3% by mass is 1-methyl in advance. -2-Pyrrolidone was added to the dissolved solution and mixed to prepare a positive electrode mixture paste. This positive electrode mixture paste was applied to one side on an aluminum foil (current collector), dried and pressure-treated, and cut into a predetermined size to prepare a strip-shaped positive electrode sheet. The density of the portion of the positive electrode excluding the current collector was 3.6 g / cm ³ . Further, silicon (single substance); 10% by mass, artificial graphite (d ₀₀₂ = 0.335 nm, negative electrode active material); 80% by mass, acetylene black (conductive agent); 5% by mass are mixed, and polyvinylidene fluoride (condensation) is prepared in advance. (Adhesive); 5% by mass was added to the solution dissolved in 1-methyl-2-pyrrolidone and mixed to prepare a negative electrode mixture paste. This negative electrode mixture paste was applied to one side on a copper foil (current collector), dried and pressure-treated, and cut into a predetermined size to prepare a negative electrode sheet. The density of the portion of the negative electrode excluding the current collector was 1.5 g / cm ³ . Further, as a result of X-ray diffraction measurement using this electrode sheet, the ratio [I (110) / I) of the peak intensity I (110) on the (110) plane and the peak intensity I (004) on the (004) plane of the graphite crystal. (004)] was 0.1. Then, the positive electrode sheet, the separator made of a microporous polyethylene film, and the negative electrode sheet were laminated in this order, and the non-aqueous electrolytic solution having the composition shown in Tables 1 and 2 was added to prepare a laminated battery.

[Evaluation of high temperature cycle characteristics]
Using the battery produced by the above method, the battery is charged in a constant temperature bath at 55 ° C. with a constant current and constant voltage of 1C to a final voltage of 4.25V for 3 hours, and then under a constant current of 1C and a discharge voltage of 3.0V. Discharging to 300 cycles was defined as one cycle, and this was repeated until 300 cycles were reached. Then, the capacity retention rate after the cycle was calculated by the following formula.
Capacity retention rate (%) = (Discharge capacity in the 300th cycle / Discharge capacity in the 1st cycle) x 100

[Discharge capacity retention rate after high temperature charge storage]
<Initial discharge capacity>
Using the laminated battery produced by the above method, the battery was charged in a constant temperature bath at 25 ° C. with a constant current and constant voltage of 1C to a final voltage of 4.35 V for 3 hours, and the temperature of the constant temperature bath was lowered to −20 ° C. The discharge was performed to a final voltage of 2.75 V under a constant current of 1C, and the initial discharge capacity at −20 ° C. was determined.
<High temperature charge storage test>
Next, this laminated battery was charged in a constant temperature bath at 65 ° C. at a constant current and constant voltage of 1C to a final voltage of 4.35V for 3 hours, and stored at 4.35V for 7 days. Then, it was placed in a constant temperature bath at 25 ° C. and once discharged to a final voltage of 2.75 V under a constant current of 1 C.
<Discharge capacity after high temperature charge storage>
After that, the discharge capacity at −20 ° C. after high-temperature charge storage was determined in the same manner as in the initial measurement of the discharge capacity.
<Capacity retention rate at -20 ° C after high-temperature charge storage>
The capacity retention rate at −20 ° C. after high-temperature charge storage was calculated by the following formula.
Discharge capacity retention rate (%) after high-temperature charge storage = (-20 ° C discharge capacity after high-temperature charge storage / initial -20 ° C discharge capacity) x 100
The battery manufacturing conditions and battery characteristics are shown in Tables 1 to 3.

Example 23 and Comparative Example 3
Instead of the positive electrode active material used in Example 1 and Comparative Example _1, using LiNi _{1/2 Mn} 3/2 _{O 4} (positive electrode active material), to produce a positive electrode sheet. _{LiNi 1/2} Mn _3/2 O ₄ coated with amorphous carbon; 94% by mass, acetylene black (conductive agent); 3% by mass is mixed, and polyvinylidene fluoride (binding agent); 3% by mass is mixed in advance. Was added to the solution dissolved in 1-methyl-2-pyrrolidone and mixed to prepare a positive electrode mixture paste. This positive electrode mixture paste was applied to one side on an aluminum foil (current collector), dried and pressurized, and cut to a predetermined size to prepare a positive electrode sheet. A laminated battery was produced in the same manner as in Example 4 and Comparative Example 1 except that the voltage was set to 4.9 V and the discharge cutoff voltage was set to 2.7 V, and the battery was evaluated. The results are shown in Table 4.

Examples 24 and 25 and Comparative Example 4
A negative electrode sheet was prepared using _{lithium titanate Li 4} Ti ₅ O ₁₂ (negative electrode active material) instead of the negative electrode active material used in Example 4 and Comparative Example 1. Lithium-titanium Li ₄ Ti ₅ O ₁₂ ; 80% by mass, acetylene black (conductive agent); 15% by mass is mixed, and polyvinylidene fluoride (binding agent); 5% by mass is converted to 1-methyl-2-pyrrolidone in advance. It was added to the dissolved solution and mixed to prepare a negative electrode mixture paste. This negative electrode mixture paste was applied to one side on a copper foil (current collector), dried and pressurized, and cut to a predetermined size to prepare a negative electrode sheet. A laminated battery was produced in the same manner as in Example 1 and Comparative Example 1, except that the voltage was set to 2.8 V, the discharge end voltage was set to 1.2 V, and the composition of the non-aqueous electrolyte solution was changed to a predetermined value. , Battery evaluation was performed. The results are shown in Table 5.

In each of the above-mentioned lithium secondary batteries of Examples 1 to 22, the compound described in Comparative Example 1 and Patent Document 1 in the case where the compound represented by compound (I) was not added to the non-aqueous electrolytic solution of the present invention was added. Compared with the lithium secondary battery of Comparative Example 2 in the case, the high temperature cycle characteristics and the high temperature and high voltage storage characteristics are improved. From the above, it was found that the effect when the power storage device of the present invention is used at a high voltage is an effect peculiar to the case where the compound (I) is contained in the non-aqueous electrolytic solution.
Further, from the comparison between Example 23 and Comparative Example 3, from _{the case where lithium manganese acid salt (LiNi 1/2} Mn _3/2 O ₄ ) was used for the positive electrode, and from the comparison between Examples 24 to 25 and Comparative Example 4, The same effect can be seen when lithium titanate (Li ₄ Ti ₅ O _{12) is used for the negative electrode.} Therefore, it is clear that the effect of the present invention does not depend on a specific positive electrode or negative electrode.

Further, the non-aqueous electrolytic solution of the present invention also has an effect of improving the discharge characteristics of the lithium primary battery in a wide temperature range.

By using the non-aqueous electrolytic solution of the present invention, it is possible to obtain a power storage device having excellent electrochemical characteristics in a wide temperature range. In particular, when used as a non-aqueous electrolyte for power storage devices such as lithium secondary batteries installed in hybrid electric vehicles, plug-in hybrid electric vehicles, battery electric vehicles, etc., power storage devices whose electrochemical characteristics do not easily deteriorate over a wide temperature range. Can be obtained.
Further, due to its special structure, the novel compound of the present invention can be used as a material for electrolytes, heat resistance, etc. in general chemistry, especially in the fields of organic chemistry, electrochemistry, biochemistry and polymer chemistry. It is useful as an intermediate raw material for electronic materials, polymer materials, etc., or as a battery material.

Claims (5)

A non-aqueous electrolyte solution in which an electrolyte salt is dissolved in a non-aqueous solvent contains an oxy compound (2-oxo-1,3-dioxolan-4-yl) represented by the following general formula (I), and the electrolyte. A non-aqueous electrolyte solution for a power storage device, wherein the salt is a lithium salt.

(In the formula, R ¹ , R ² and R ³ are hydrogen atoms and n represents 1 or 2. When n is 1, L ¹ is -C (= O) -R ⁴ or -S (= O). ) _2- R ⁵ is indicated, and when n is 2, L ¹ indicates −C (= O) C (= O) −. R ⁴ is an alkyl group having 1 to 6 carbon atoms and 3 to 6 carbon atoms. cycloalkyl group, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryl group having 6 to 12 carbon atoms, or alkoxycarbonyl of 2 to 6 carbon atoms .R a group ⁵ is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, 7 to 13 carbon atoms shown aralkyl group, or an aryl group having 6 to 12 carbon atoms.) The (2-oxo-1,3-dioxolane-4-yl) oxy compound represented by the general formula (I) is 2-oxo-1,3-dioxolan-4-yl acetate, 2-oxo-1,2, 3-Dioxolane-4-yl acrylate, 2-oxo-1,3-dioxolan-4-yl methacrylate, methyl (2-oxo-1,3-dioxolan-4-yl) oxalate, ethyl (2-oxo-1, 3-Dioxolane-4-yl) oxalate, bis (2-oxo-1,3-dioxolan-4-yl) oxalate , 2-oxo-1,3-dioxolan-4-yl methanesulfonate, and 2-oxo-1 The non-aqueous electrolyte solution for a power storage device according to claim 1, which is one or more selected from 3-dioxolane-4-ylethenesulfonate. A storage device including a positive electrode, a negative electrode, and a non-aqueous electrolytic solution in which an electrolyte salt is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolytic solution is the non-aqueous electrolytic solution according to claim 1 or 2. Power storage device. An oxy compound represented by the following general formula (II) (2-oxo-1,3-dioxolane-4-yl).

(In the formula, R ⁸ , R ² and R ³ are hydrogen atoms and n represents 1 or 2. When n is 1, L ² is -C (= O) -R ⁹ or -S (=). O) ₂ −R ⁵ and when n is 2, L ² represents −C (= O) C (= O) −. R ⁹ is a cycloalkyl group having 3 to 6 carbon atoms and 2 carbon atoms. 6 alkynyl group, an aralkyl group having 7 to 13 carbon atoms, an aryl group having 6 to 12 carbon atoms, or .R ⁵ showing the alkoxycarbonyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, shown alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) 2 -oxo-1,3-dioxolane-4-yl acrylate, 2-oxo-1,3-dioxolan-4-yl methacrylate, methyl (2-oxo-1,3-dioxolan-4-yl) oxalate, ethyl ( 2-oxo-1,3-dioxolane-4-yl) oxalate, bis (2-oxo-1,3-dioxolan-4-yl) oxalate , 2-oxo-1,3-dioxolane-4-yl methanesulfonate, And the (2-oxo-1,3-dioxolane-4-yl) oxy compound according to claim 4, which is selected from 2-oxo-1,3-dioxolane-4-yl ethensulfonate.