TW494597B - Electrolyte and compound used in battery and its preparation method - Google Patents

Abstract

This invention provides a novel use of methylene-bridged diesters, especially the use of methylene-bridged diesters as solvents in the electrolyte of lithium battery; meanwhile the said new diester compound bridged by methylene are also described. An electrolyte contains conductive salts of lithium cation or quaternary ammonium cation and one or more methylene-bridged diester compounds with formula (I): R1C(O)OCR2R3OC(O)R4, in which R1, R4 can be the same or different and are independently 2-4C alkyl or 1-4C fluoroalkyl, R2 and R3 can be the same or different, R2 is hydrogen (H), and R3 is H or methyl.

Description

494597 V. Description of the invention (1 ·) The present invention relates to the new application feasibility of a diester and a new compound using methylene as a bridge. Lithium-ion batteries have an electrolyte that contains a conductive salt and a dehydrating agent that does not contain protons to the solute and does not accept protons from the solute. LiPF0 is a very good conductive salt, although other cations such as fourth-order Onium-Ionen can also be used. Other lithium salts that can be used are LiBF4, the lithium salt of TrifluormethansulfonSure, or the lithium salt of Bis- (tnfluormethansulfonyl) imid. As the solvent, for example, Alkylencarbonate, ethers, Formamide, Sulfolane, or Methylsulfolane are used. Also available are specific nitriles or nitrogen-containing compounds, such as nitromethane, pyrrolidone and the like, see, for example, Macoto Ue, Kazuhiko Ida and Shoichiro Mori in J. Electrochem · Soc · 141 (1994), pages 2989 to 2996. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics The task of the present invention is to identify other compounds that can be used as electrolyte solvents. This task is also successfully accomplished by the present invention. The compound of the general formula (I) according to the present invention, rLcxokk ^ rLo-cxohi4, wherein R1 and R4 are the same or different, and represent that the alkynyl or fluorene containing one to four carbon atoms is replaced by at least one gas atom. A sintered group containing one to four carbon atoms, and R2 and R3 are the same or different, R2 represents hydrogen, and R3 represents chlorine or CH3, as a solvent in an electrolyte, especially an electrolyte of a lithium ion battery. R and R have the same preferences than their fathers' and represent CF3. R2 and R3 are mainly the same and represent hydrogen.

494597

V. Description of the invention (2 ·) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Although the compound of formula (I) can be used as a single solvent in the electrolyte. However, it is preferred to use a compound of formula (I) together with at least one other organic solvent that neither protons nor accepts protons from the solute. Conventional electrolyte solvents can also be used as other solvents. The types of solvents that can be used are mentioned, for example, in literature references stated by authors such as Ue. Particularly useful are Alkylencarbonate, Lactone, Nitrile, and Formamide. It is also very beneficial to mix them with difluorinated amines such as trifluoroacetic acid. "Alkyl group, which here mainly represents an alkyl group containing one to four carbon atoms. The molar number ratio between the compound of formula ① and the solvent compound is in the range of 1: 1 to 1:10. In addition to these solvent mixtures, the electrolyte is also the subject of the present invention. The electrolyte contains a compound of general formula (I) and conductive salts, and other conventional electrolyte solvents when necessary. Preferred conductive salts include as cations. Although lithium cations such as quaternary ammonium cations can also be used. Preferred conductive salt anions have an anion PF6 with a negative charge, but anions with a negative charge that can be used are BF4, CF3S03, C104 or [N (S〇2CF: 3) 2]. It is preferred that the electrolyte according to the present invention contains another electrolyte solvent, mainly an alkylene carboxylate (Alkylencarbonat) or n, N of trifluoroacetic acid. _Dialkylammoniums, in which the alkyl group represents an alkyl group containing one to three carbon atoms. It can also be used as other electrolyte solvents. In the amines, the nitrogen on the amidine group is inserted into a five- or six-ring system, and the ring system can also contain heteroatoms like oxygen. For example, amidines of trifluoroacetic acid, Paper size applies to China National Standard (CNS) A4 (2lfi_97mm) -6 'T1-^ II I ---- ί II I--It ·! · (Please read the precautions on the back before filling this page ) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 494597 A7 ^-E_ — V. Description of the invention (3.) The amino group in the invention is made of Pyrrolidnyl-, MorphUnyl Piperidinyl-. Some compounds of the general formula (1) are novel. Compounds of the general formula (I), where R1, R2, R3 and R4 have the above-mentioned representative meaning, and compounds, where R1 and R4 The exception is CHS. The same subject matter of the present invention is CF3_C (0) -0-CH2_0-C (0) -CF3, which is a fairly preferred compound. To synthesize a compound of general formula (I) to have a chemical structural formula Preparation of r2r3c (〇) 'The riot polymer or polymer of this preparation will have the chemical structure formula 1 ^-(:( 0) -0 (0) -011 in the presence of a catalytic amount of acid The anhydride of 4 is transformed. The substituted R1, R2, R3, and R4 have the representative meanings described above. Technology 'especially refers to the solvents that can be used in this series, especially the battery electrolyte will be further enriched by the present invention. The following examples are intended to further illustrate the present invention, but not to limit it to its scope. Example Example 1: Synthesis of methylene-di- [trifluoroacetate] (-CH2-0_) n + n (CF3C0) 20 This nCH2 (OOCCF3) 2 was suspended in 100 ml of liver trifluoroacetate in a round bottom reaction bottle connected to a reflux condenser. After adding a catalytic amount of concentrated sulfuric acid, the reaction mixture was heated under reflux condensation. The reaction This paper size applies to China National Standard (CNS) A4 (210 X 297 Public Love) -7-

«J * ---- ----- tr --------- line ®- (Please read the notes on the back before filling this page) 494597 A7 B7 V. Description of the invention (4 ·) in It ends in about an hour. The crude product obtained by the reaction was purified by detailed distillation. Methylene-di- "trifluoroacetate"

Yield: Κρ: ^ -NMR 13

C-NMR 45.43 g 68-70 ° C at 10 mbar 5.65 ppm (Singulett, CH2) 90.99 ppm (Singulett, CH2) 115.15 ppm (Quartett 5 CF3) 157.56 ppm (Quartett 5 CO) -76.98 ppm (Singulett? CF3) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

494597 Scope of Patent Application No. 89122080 Patent Application Amendment of Scope of Patent This kind of tritium solution includes conductive salts having a bell cation or a quaternary ammonium cation and one or more compounds of the general formula ①, where R1 and R4 are the same or different and represent one containing four to four carbon atoms. An alkyl group or an alkyl group containing one to four carbon atoms substituted by at least one fluorine atom, R2 and R3 are the same or different, R2 represents chlorine and R represents wind or CH3 'as a solvent in the electrolyte. / · • According to the electrolyte described in item 1 of the scope of the patent application, where “and M are the same and represent CF3. .1 According to the electrolyte described in the scope of the patent application, item 2 or item 2, where R 2 and R 3 are the same and Represents 4. 4. The electrolyte according to item 1 of the scope of the patent application, which includes LiPF6 as a conductive salt. ^ 5. The electrolyte according to item 1 of the scope of the patent application, which is then included to JNeither Glutton does not contain a water-containing electrolyte solvent that does not accept protons from the solute. 6. A compound of general formula (I), Rl-C (〇y〇 ^ CR2R3 ^ C (〇y ^ National Standard (CNS) A4) Specifications (210 X 297 mm) -9- -------- Order --- I ---- ** ^ · CPlease read the notes on the back before filling in this page} 494597 A8 B8 C8 D8 6. The scope of the patent application, where R1 and R4 are the same or different, and represent an alkyl group containing 2 to 4 carbon atoms or an alkyl group containing one to four carbon atoms substituted with at least one fluorine atom, R2 and R3 is the same or different, r2 represents hydrogen and R3 represents hydrogen or CH3. 7 · —A method for preparing compounds of general formula (I), r, c (〇) _〇_C R2R3-〇_c (0) -R4 wherein R1 and R4 are the same or different, and represent an alkyl group containing 2 to 4 carbon atoms or a group containing one to four carbon atoms substituted with at least one fluorine atom Alkyl, R2 and R3 are the same or different, R2 represents hydrogen and R3 represents hydrogen or a%, the aldehydes with the chemical structure formula R2R3c (〇), or the oligomers or polymers of the aldehydes have catalytic properties The anhydride with the chemical structure formula RLC (0) _〇 (〇) _c_R4 will be converted in the presence of the amount of acid. -------- tr --------- $ · (please first (Please read the notes on the back before filling out this page) Print a moderate piece of paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (α quasi-standard inspection-