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Nonaqueous electrolytic solution including ester having 3,3,3-trifluoropropionate group and nonaqueous electrolyte battery using same

A non-aqueous electrolyte, trifluoropropionate technology, applied in non-aqueous electrolyte batteries, non-aqueous electrolytes, organic electrolytes and other directions, can solve the problems of reduced battery characteristics, low stability of polymer coating, and deterioration of battery capacity, etc. Achieve the effect of suppressing gas generation, excellent oxidation resistance, and suppressing capacity deterioration

Inactive Publication Date: 2017-03-22
KANTO DENKA IND CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in this method, the reactivity of the electrode is also increased, so there is a problem that the non-aqueous electrolyte solution, as described above, undergoes an oxidation / reduction reaction with the positive electrode and the negative electrode, causing a decrease in cycle characteristics, and battery characteristics during storage in a charged state. reduce
[0011] However, fluorinated cyclic carbonates such as 4-fluoroethylene carbonate have lower stability of the polymer coating than vinylene carbonate, which is generally known as an additive for forming a polymer coating on the negative electrode. Deterioration of battery capacity due to reformation reaction of the polymerized coating, gas generation during long-term storage, and high-temperature storage are problems
In addition, the above-mentioned vinylene carbonate is an excellent polymerization film-forming additive, but its oxidation resistance is poor, so the oxidative decomposition reaction on the positive electrode side becomes a problem.

Method used

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  • Nonaqueous electrolytic solution including ester having 3,3,3-trifluoropropionate group and nonaqueous electrolyte battery using same
  • Nonaqueous electrolytic solution including ester having 3,3,3-trifluoropropionate group and nonaqueous electrolyte battery using same
  • Nonaqueous electrolytic solution including ester having 3,3,3-trifluoropropionate group and nonaqueous electrolyte battery using same

Examples

Experimental program
Comparison scheme
Effect test

manufacture example 1

[0062]

[0063] In a 50 mL reaction apparatus equipped with a fractionator, 6.10 g (98.3 mmol) of ethylene glycol and 28.2 g (220 mmol) of 3,3,3-trifluoropropionic acid were mixed. 0.21 g (2.1 mmol) of 95% sulfuric acid was added to the mixture, and the reaction was carried out while heating the temperature in the reaction apparatus to 100° C. under reduced pressure (30 kPa) and distilling off water. After reacting for 7 hours, it was cooled to room temperature, and 50 mL of water was added to the reaction product, followed by stirring. The organic phase was separated and washed with 100 mL of 5% sodium bicarbonate water to obtain a crude product of ethylene bis(3,3,3-trifluoropropionate) as a colorless clear liquid. Yield 24.3 g, 85% yield. As a result of measurement by gas chromatography, the gas chromatogram area of ​​ethylene bis(3,3,3-trifluoropropionate) was 97.2%. The crude product was purified by precision distillation under reduced pressure (Snyder 5 sphere, 0.25 ...

manufacture example 2

[0069]

[0070] In a 50 mL reaction apparatus equipped with a fractionator, 8.11 g (90.0 mmol) of 1,4-butanediol and 23.9 g (187 mmol) of 3,3,3-trifluoropropionic acid were mixed. 0.16 g (1.7 mmol) of 95% sulfuric acid was added to the mixture, and the temperature in the reaction apparatus was heated to 120° C. under reduced pressure (40 kPa), and the reaction was carried out while distilling off water. After reacting for 8 hours, it was cooled to room temperature, and 50 mL of water was added to the reaction product, followed by stirring. The organic phase was separated and washed with 100 mL of 5% sodium bicarbonate water to obtain a crude product of tetramethylenebis(3,3,3-trifluoropropionate) as a light brown liquid. Yield 23.4 g, 84% yield. As a result of measurement by gas chromatography, the gas chromatogram area of ​​tetramethylenebis(3,3,3-trifluoropropionate) was 97.3%. The crude product was purified by precision distillation under reduced pressure (Snyder 5 sphe...

Embodiment 1

[0076] Ethylene bis(3,3,3-trifluoropropionate) represented by formula 2 produced in Production Example 1 was mixed with 97 wt% of propylene carbonate (PC) so as to be 3 wt%, to prepare a non-aqueous system solvent. Lithium hexafluorophosphate LiPF as electrolyte 6 It was dissolved in this non-aqueous solvent at a ratio of 1 mol / L to prepare a non-aqueous electrolytic solution. Using this non-aqueous electrolyte, making figure 1 The three-electrode test cell shown.

[0077] In the above-mentioned three-electrode battery cell, a sealed three-electrode battery cell manufactured by Keihin Rika Kogyo Co., Ltd. was used, and a natural graphite-coated electrode sheet (negative electrode single layer) manufactured by Piotrek Co., Ltd. was used as the working electrode 1 and cut to a specified size. For the obtained material, lithium metal was used for the counter electrode 2 and the reference electrode 3 , and the separator 4 was interposed between these electrodes, and immersed i...

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Abstract

Provided are a secondary battery nonaqueous electrolytic solution that has excellent oxidation resistance, that suppresses a reaction between the nonaqueous electrolytic solution and an electrode, that suppresses decomposition even under high-voltage conditions, and that can suppress capacity deterioration of the secondary battery and gas generation therein, as well as a nonaqueous electrolyte secondary battery using the nonaqueous electrolytic solution. Provided is a secondary battery nonaqueous electrolytic solution characterized by including a nonaqueous solvent including an ester having a 3,3,3-trifluoropropionate group represented by formula 1, a fluorinated cyclic carbonate that is a 4-fluoroethylene carbonate (FEC) or a derivative thereof, and at least one selected from among a cyclic carbonate, a chain carbonate, and a fluorinated chain carboxylic acid ester; and a lithium salt serving as an electrolyte.

Description

technical field [0001] The invention relates to a novel nonaqueous electrolytic solution and a nonaqueous electrolytic solution secondary battery containing the nonaqueous electrolytic solution. In particular, it relates to a non-aqueous electrolytic solution as described below, and a non-aqueous electrolytic solution secondary battery using the non-aqueous electrolytic solution. Esters of 3,3-trifluoropropionate groups; fluorinated cyclic carbonates which are 4-fluoroethylene carbonate (FEC) or derivatives thereof; and At least one of ester, chain carbonate and fluorinated chain carboxylate. [0002] [0003] (In Formula 1, n represents an integer of 1 to 20) Background technique [0004] Conventionally, non-aqueous electrolyte secondary batteries such as lithium secondary batteries used as power sources for so-called portable electronic devices such as mobile phones and notebook computers have been increasingly used in driving vehicles such as automobiles due to the h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0567H01M10/0569
CPCH01M10/052H01M10/0567H01M10/0569H01M2300/0028Y02E60/10H01M10/0525H01M2300/004
Inventor 大前理冈本敏明
Owner KANTO DENKA IND CO LTD
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