JP2007084469A - Carbonic acid ester compound, electrolyte, electric battery, and method for production of carbonic acid ester compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a labeled carbonic acid ester compound and a method for producing the same and to provide an electrolyte and an electric battery containing the labeled carbonic acid ester. <P>SOLUTION: The invention relates to the carbonic acid ester compounds such as 1, 3-dioxole-2-on, 4-fluoro-1, 3-dioxorane-2-on, 4-chloro-1, 3-dioxorane-2-on or dimethylcarbonate, etc., wherein at least a part of the constituting elements are substituted with deuterium,<SP>13</SP>C,<SP>17</SP>O or<SP>18</SP>O. The compounds are labeled and working mechanisms of the electric battery can be studied by mixing the compounds with the electrolyte of the battery and analyzing the decomposed product in the battery. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a carbonate ester compound and a method for producing the same, and an electrolyte and a battery including the carbonate ester compound.

  In recent years, many portable electronic devices such as a camera-integrated VTR (Videotape Recorder), a digital still camera, a mobile phone, a portable information terminal, or a notebook personal computer have appeared, and the size and weight of the portable electronic device have been reduced. Accordingly, development of secondary batteries that are lightweight and can obtain a high energy density as power sources for these electronic devices has been underway. Among these, lithium ion secondary batteries using a carbon material for the negative electrode, a composite material of lithium and a transition metal for the positive electrode, and a carbonate ester for the electrolyte are larger than conventional lead batteries and nickel cadmium batteries. Since energy density can be obtained, it is widely used.

In such a lithium ion secondary battery, since the negative electrode becomes a strong reducing agent in the charged state, the electrolytic solution is easily decomposed, and the discharge capacity is accordingly reduced. Therefore, various studies have been made on the composition of the electrolytic solution in order to improve battery characteristics such as cycle characteristics. For example, the use of 1,3-dioxol-2-one, 4-fluoro-1,3-dioxolan-2-one, or the like as an additive or solvent has been studied (for example, see Patent Documents 1 and 2). .
JP-A-8-45545 Japanese Patent Laid-Open No. 7-240232

  These additives or solvents are thought to suppress further decomposition of the electrolytic solution by decomposing to form a film on the electrode surface, but it is possible to use a plurality of carbonates as additives or solvents. In many cases, it is unclear what kind of additive or solvent works inside the battery.

  The present invention has been made in view of such problems, and an object thereof is to provide a labeled carbonate compound and a method for producing the same, and an electrolyte and a battery including the labeled carbonate compound.

In the carbonate ester compound of the present invention, at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O or ¹⁸ O.

The first carbonic acid ester compound production method of the present invention comprises an alcohol containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O in at least a part of the constituent elements, phosgene, triphosgene, halogenated formate, carbonic acid. A step of reacting at least one member selected from the group consisting of an ester and a halogenated carbonate.

The second method for producing a carbonic acid ester compound of the present invention includes a step of reacting at least a part of the constituent elements with alkylene oxide containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O and carbon dioxide. It is a waste.

The third method for producing a carbonic acid ester compound of the present invention comprises a step of halogenating a carbonic acid ester containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O in at least a part of the constituent elements with a halogenating agent. Is included.

Manufacturing method of the fourth carbonate compound of the present invention, at least a portion of the constituent elements, deuterium, a halogen of the halogenated carbonic esters containing ¹³ C, ¹⁷ O or ¹⁸ O, by halogen exchange reaction, It includes a step of substituting with another halogen.

In the fifth method for producing a carbonate ester compound of the present invention, a halogenated carbonate containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O as at least a part of constituent elements is dehalogenated using a base. It includes a step of forming an unsaturated bond by hydrogenation.

The electrolyte of the present invention contains a carbonate compound in which at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O.

The battery of the present invention includes an electrolyte together with a positive electrode and a negative electrode, and the electrolyte contains a carbonate compound in which at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O. It is a waste.

According to the carbonate ester compound of the present invention, since at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O, it can be labeled with these elements. Therefore, according to the electrolyte or battery of the present invention containing the carbonate ester compound, for example, the operating mechanism can be investigated by analyzing decomposition products in the inside thereof.

Further, according to the method for producing a carbonate compound of the present invention, an alcohol containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O in at least a part of the constituent elements, phosgene, triphosgene, halogenated formate, Since it includes a step of reacting at least one member selected from the group consisting of a carbonate ester and a halogenated carbonate ester, or at least a part of the constituent elements, deuterium, ¹³ C, ¹⁷ O or ¹⁸ O Or a carbonic acid ester containing deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O as at least a part of the constituent elements is halogenated. since to include the step of halogenated agents, or at least some of the constituent elements, deuterium, ¹³ C, ¹⁷ O or ¹⁸ Halogen halogenated carbonate containing, by halogen exchange reaction, at least a portion of the since to include the step of substituting other halogen, or an element, deuterium, ¹³ C, ¹⁷ O or ¹⁸ Since the halogenated carbonate containing O contains a step of forming an unsaturated bond by dehydrohalogenation using a base, the carbonate compound of the present invention can be easily produced.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

In the carbonate compound according to one embodiment of the present invention, at least a part of the constituent elements in the carbonate ester or the halogenated carbonate ester is deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O, which is an isotope element. It is what. Thereby, it can label. In general, hydrogen (H), carbon (C), and oxygen (O) as constituent elements such as carbonate ester are present as ¹ H, ¹² C, ¹⁶ O.

  Such a carbonic acid ester compound is, for example, a chain compound, a cyclic compound, or an unsaturated compound. Specifically, the compound shown in Chemical Formula 1 or the compound shown in Chemical Formula 2 can be used.

In Chemical Formula 1, R1 and R2 represent a hydrocarbon group or a group in which at least a part of hydrogen is substituted with halogen. R1 and R2 may be the same or different. However, at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ C, or ¹⁸ O. Specific examples of R1 and R2 include a methyl group, an ethyl group, a propyl group, a butyl group, or a group obtained by substituting at least a part of these hydrogens with a halogen such as fluorine or chlorine.

In Chemical Formula 2, R3 represents a hydrocarbon group having a single bond between carbons or a double bond between carbons, or a group obtained by substituting at least a part of hydrogen with a halogen. However, at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ C, or ¹⁸ O. Specific examples of R3 include an ethylene group or a group obtained by substituting at least a part of hydrogen with a halogen such as fluorine or chlorine, a propylene group, a vinylene group, or a phenylene group. )

Specific examples of such carbonate compounds include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, dibutyl carbonate, dimethyl fluorocarbonate containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O as constituent elements. , Diethyl fluorocarbonate, ethyl methyl fluorocarbonate, dipropyl fluorocarbonate, dibutyl fluorocarbonate, 1,3-dioxolan-2-one (ethylene carbonate), 1,3-dioxol-2-one (vinylene carbonate), 4-fluoro- Examples include 1,3-dioxolan-2-one, 4-chloro-1,3-dioxolan-2-one, 4,5-difluoro-1,3-dioxolan-2-one, and catechol carbonate.

  The carbonate compound can be produced, for example, as follows.

For example, by reacting an alcohol in which at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O or ¹⁸ O with phosgene, triphosgene, halogenated formate, carbonate or halogenated carbonate. Can be manufactured. Examples of the alcohol include methanol, ethanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, and deuterium, ¹³ C, ¹⁷ O or ¹⁸ O as constituent elements. Examples thereof include monohydric alcohols such as phenol, and dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, and catechol. Further, when phosgene, triphosgene, or halogenated formate is reacted, a trapping agent may be used to capture hydrogen halide such as hydrogen chloride to be generated. Examples of the trapping agent include amines such as pyridine and triethylamine. When a carbonate ester or a halogenated carbonate ester is reacted, an ester exchange reaction is performed. Therefore, an acid such as hydrochloric acid or sulfuric acid, or a base such as an alkali metal hydroxide may be used as a catalyst.

Moreover, you may manufacture a carbonate ester compound as follows. For example, a cyclic carbonate compound can be produced by reacting carbon dioxide with alkylene oxide containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O as at least a part of the constituent elements. . Examples of the alkylene oxide include ethylene oxide, propylene oxide, and epoxy butane containing deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O as a constituent element. In the reaction, a catalyst may be used as necessary. Examples of the catalyst include metal halide salts.

Furthermore, you may manufacture a carbonate ester compound as follows. For example, at least a part of the constituent elements can be produced by halogenating a carbonate ester having deuterium, ¹³ C, ¹⁷ O or ¹⁸ O using a halogenating agent. Examples of the halogenating agent include halogen alone, sulfuryl chloride, thionyl chloride, or halogenated succinimide. Moreover, a radical initiator or a catalyst may be used as necessary, and light irradiation may be performed.

Furthermore, you may manufacture a carbonate ester compound as follows. For example manufacturing, for at least some of the constituent elements, deuterium, halogen ¹³ C, ¹⁷ O or ¹⁸ O and the halogenated carbonate, by utilizing the halogen exchange reaction, by substituting other halogen can do. Specifically, by treating a carbonic acid ester compound having chlorine with a halogen exchange agent, for example, potassium fluoride as a fluorinating agent, a carbonic acid ester compound having fluorine can be produced.

In addition, the carbonate ester compound can be produced as follows. For example, at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O, and further, a carbonate ester having a halogen atom is dehydrohalogenated using a base to form an unsaturated bond. The carbonic acid ester compound which has can be manufactured. Examples of the base include amines such as trimethylamine and pyridine, or alkali metal hydroxides.

  The carbonate compound can be used for a secondary battery as follows, for example.

  FIG. 1 shows a cross-sectional structure of the secondary battery. This secondary battery is called a so-called cylindrical type, and a winding in which a strip-like positive electrode 21 and a strip-like negative electrode 22 are laminated and wound inside a substantially hollow cylindrical battery can 11 via a separator 23. An electrode body 20 is provided. The battery can 11 is made of, for example, iron (Fe) plated with nickel (Ni), and has one end closed and the other end open. An electrolytic solution is injected into the battery can 11 and impregnated in the separator 23. In addition, a pair of insulating plates 12 and 13 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.

  At the open end of the battery can 11, a battery lid 14, a safety valve mechanism 15 provided inside the battery lid 14, and a thermal resistance element (Positive Temperature Coefficient; PTC element) 16 are interposed via a gasket 17. It is attached by caulking, and the inside of the battery can 11 is sealed. The battery lid 14 is made of, for example, the same material as the battery can 11. The safety valve mechanism 15 is electrically connected to the battery lid 14 via the heat sensitive resistance element 16, and the disk plate 15A is reversed when the internal pressure of the battery exceeds a certain level due to an internal short circuit or external heating. Thus, the electrical connection between the battery lid 14 and the wound electrode body 20 is cut off. When the temperature rises, the heat sensitive resistance element 16 limits the current by increasing the resistance value and prevents abnormal heat generation due to a large current. The gasket 17 is made of, for example, an insulating material, and asphalt is applied to the surface.

  For example, a center pin 24 is inserted in the center of the wound electrode body 20. A positive electrode lead 25 made of aluminum (Al) or the like is connected to the positive electrode 21 of the spirally wound electrode body 20, and a negative electrode lead 26 made of nickel or the like is connected to the negative electrode 22. The positive electrode lead 25 is electrically connected to the battery lid 14 by being welded to the safety valve mechanism 15, and the negative electrode lead 26 is welded to and electrically connected to the battery can 11.

  FIG. 2 shows an enlarged part of the spirally wound electrode body 20 shown in FIG. The positive electrode 21 has, for example, a structure in which a positive electrode active material layer 21B is provided on both surfaces or one surface of a positive electrode current collector 21A having a pair of opposed surfaces. The positive electrode current collector 21A is made of, for example, a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil.

The positive electrode active material layer 21B includes, for example, any one or more of positive electrode materials capable of inserting and extracting lithium (Li) as a positive electrode active material, and a conductive agent such as a carbon material as necessary. And a binder such as polyvinylidene fluoride. The positive electrode material capable of inserting and extracting lithium does not contain lithium such as titanium sulfide (TiS ₂ ), molybdenum sulfide (MoS ₂ ), niobium selenide (NbSe ₂ ), or vanadium oxide (V ₂ O ₅ ). Chalcogenide, or lithium cobalt composite oxide (Li _x CoO ₂ (0.05 ≦ x ≦ 1.10)), lithium nickel composite oxide (Li _x NiO ₂ ), lithium nickel cobalt composite oxide (Li _x Ni _1-z Co _z O ₂ (z <1)), lithium nickel cobalt manganese composite oxide (Li _x Ni _(1-vw) Co _v Mn _w O 2 (v + w <1)), lithium manganese composite having a spinel structure oxide (LiMn ₂ O _4), lithium iron phosphate compound (LiFePO _4), a lithium iron manganese phosphate compound (LiFe _1-u Mn u P ₄ (u <1)) lithium-containing compound containing lithium and the like.

  The negative electrode 22 has, for example, a structure in which a negative electrode active material layer 22B is provided on both surfaces or both surfaces of a negative electrode current collector 22A having a pair of opposed surfaces, similarly to the positive electrode 21. The anode current collector 22A is made of, for example, a metal foil such as a copper foil.

  The negative electrode active material layer 22B includes, for example, any one or more of negative electrode materials capable of inserting and extracting lithium as a negative electrode active material. An adhesive may be included. Examples of the negative electrode material capable of occluding and releasing lithium include a carbon material capable of occluding and releasing lithium. Examples of the carbon material include any one or two of non-graphitizable carbon, graphitizable carbon, graphite, pyrolytic carbon, coke, glassy carbon, organic polymer compound fired body, activated carbon, and carbon black. The above can be used. Among these, cokes include pitch coke, needle coke, and petroleum coke. Organic polymer compound fired bodies are carbonized by firing polymer compounds such as phenol resin and furan resin at an appropriate temperature. What you did.

  Examples of the negative electrode material capable of inserting and extracting lithium include materials containing tin (Sn) or silicon (Si) as a constituent element. Tin and silicon are preferable because they have a large ability to occlude and release lithium and can obtain a high energy density.

  As such a negative electrode material, specifically, a simple substance, an alloy, or a compound of tin, a simple substance, an alloy, or a compound of silicon, or a material having one or more phases thereof at least in part. Is mentioned. In the present invention, alloys include those containing one or more metal elements and one or more metalloid elements in addition to those composed of two or more metal elements. Moreover, the nonmetallic element may be included. There are structures in which a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or two or more of them coexist.

  As a negative electrode material capable of inserting and extracting lithium, for example, a material containing another metal element or other metalloid element capable of forming an alloy with lithium as a constituent element can also be used. Examples of such metal elements or metalloid elements include magnesium (Mg), boron (B), aluminum, gallium (Ga), indium (In), germanium (Ge), lead (Pb), bismuth (Bi), and cadmium. (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd), or platinum (Pt).

  The separator 23 separates the positive electrode 21 and the negative electrode 22 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes. The separator 23 is made of, for example, a porous film made of synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, or a porous film made of ceramic, and has a structure in which two or more kinds of porous films are laminated. It may be said.

  The electrolytic solution impregnated in the separator 23 includes a solvent and an electrolyte salt dissolved in the solvent.

The solvent contains the carbonate ester compound of the present invention. Thereby, for example, if the battery is disassembled and a decomposition product is analyzed, the operation mechanism and the like can be clarified. Further, for example, by analyzing the amount of deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O in the film formed on the electrode, the optimal amount of the carbonate compound, the initial charge condition, and the like can be clarified.

  As the solvent, in addition to the carbonate compound, other solvents may be mixed and used. The other solvent is preferably an aprotic solvent capable of dissolving the electrolyte salt, and examples thereof include esters such as carbonate esters, ethers, lactones, nitriles, amides, and sulfones. Specifically, 1,3-dioxol-2-one (ethylene carbonate), propylene carbonate, butylene carbonate, 1,3-dioxol-2-one (vinylene carbonate), γ-butyrolactone, γ-valerolactone, diethyl carbonate Dimethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, acetate ester, butyrate ester, propionate ester, acetonitrile, Nonaqueous solvents such as glutaronitrile, adiponitrile, methoxyacetonitrile, 4-fluoro-1,3-dioxolan-2-one, or 4-chloro-1,3-dioxolan-2-one are listed. As the other solvent, one kind may be used alone, or a plurality kinds may be mixed and used.

Examples of the electrolyte salt include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium perchlorate (LiClO ₄ ), trifluoro. Lithium methanesulfonate (LiCF ₃ SO ₃ ), bis [trifluoromethanesulfonyl] imidolithium ((CF ₃ SO ₂ ) ₂ NLi), tris (trifluoromethanesulfonyl) methyllithium ((CF ₃ SO ₂ ) ₃ CLi), tris Lithium pentafluoroethyl trifluorophosphate (LiP (C ₂ F ₅ ) ₃ F ₃ ), lithium trifluoromethyl trifluoroborate (LiB (CF ₃ ) F ₃ ), lithium pentafluoroethyl trifluoroborate (LiB (C ₂ F ₅₎ F _3), or bis [pentafluoroethanesulfonyl] Bromide lithium salt such as lithium _{((C 2 F 5 SO 2} ) 2 NLi) and the like. As the electrolyte salt, one kind may be used alone, or two or more kinds may be mixed and used.

  For example, the secondary battery can be manufactured as follows.

  First, for example, the positive electrode active material layer 21B is formed on the positive electrode current collector 21A to produce the positive electrode 21. The positive electrode active material layer 21B is prepared, for example, by mixing a positive electrode active material powder, a conductive agent, and a binder to prepare a positive electrode mixture, and then using the positive electrode mixture in a solvent such as N-methyl-2-pyrrolidone. The positive electrode mixture slurry is dispersed to form a positive electrode mixture slurry, and the positive electrode mixture slurry is applied to the positive electrode current collector 21A, dried, and compression molded. Further, for example, in the same manner as the positive electrode 21, the negative electrode active material layer 22 </ b> B is formed on the negative electrode current collector 22 </ b> A to produce the negative electrode 22.

  Next, the positive electrode lead 25 is attached to the positive electrode current collector 21A by welding or the like, and the negative electrode lead 26 is attached to the negative electrode current collector 22A by welding or the like. Subsequently, the positive electrode 21 and the negative electrode 22 are wound through the separator 23, and the tip of the positive electrode lead 25 is welded to the safety valve mechanism 15, and the tip of the negative electrode lead 26 is welded to the battery can 11. The positive electrode 21 and the negative electrode 22 are sandwiched between a pair of insulating plates 12 and 13 and stored in the battery can 11. After the positive electrode 21 and the negative electrode 22 are accommodated in the battery can 11, the electrolytic solution is injected into the battery can 11 and impregnated in the separator 23. After that, the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are fixed to the opening end of the battery can 11 by caulking through a gasket 17. Thereby, the secondary battery shown in FIGS. 1 and 2 is completed.

Thus, according to the present embodiment, since at least a part of the constituent elements in the carbonate ester or halogenated carbonate ester is deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O, labeling with these elements is performed. can do. Therefore, according to the secondary battery according to the present embodiment, for example, the operating mechanism can be examined by analyzing a decomposition product in the inside.

In addition, according to the method for producing a carbonate compound according to the present embodiment, an alcohol containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O in at least a part of the constituent elements, phosgene, triphosgene, halogenated Since it includes a step of reacting at least one of the group consisting of formate ester, carbonate ester and halogenated carbonate ester, or at least part of the constituent elements, deuterium, ¹³ C, ¹⁷ O Or a step of reacting an alkylene oxide containing ¹⁸ O with carbon dioxide, or a carbonate ester containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O as at least a part of the constituent elements. , since to include the step of halogenated by using a halogenating agent, or at least a portion of the constituent elements, deuterium, ¹³ C, ¹⁷ Or halogen of the halogenated carbonic esters containing ¹⁸ O, by halogen exchange reaction, at least a portion of the since to include the step of substituting other halogen, or an element, deuterium, ¹³ C, ¹⁷ Since the halogenated carbonate containing O or ¹⁸ O includes a step of forming an unsaturated bond by dehydrohalogenation using a base, the carbonate ester compound according to the present embodiment can be easily prepared. Can be manufactured.

  Further, specific embodiments of the present invention will be described in detail.

Example 1
[Synthesis of deuterated 4-chloro-1,3-dioxolan-2-one]
A flask equipped with two condensers and two dropping funnels was replaced with nitrogen, and 4.0 g (43 mmol) of deuterated 1,3-dioxolan-2-one was placed therein, and the mixture was heated and stirred at 80 ° C. Thereafter, 7.0 g (52 mmol) of sulfuryl chloride as a halogenating agent was added dropwise simultaneously over 5 minutes while adding dropwise a chlorobenzene solution of 0.02 g (0.12 mmol) of azobisisobutyronitrile. Further, after stirring for 1 hour, diethyl ether and saturated brine were added to the reaction solution, and the organic layer was separated. Subsequently, the organic layer was dried over magnesium sulfate (MgSO ₄ ), filtered, and then distilled under reduced pressure to give 4-chloro-1,3-dioxolan-2-one (boiling point: 64 ° C. to 69.5 ° C./0.00%). (5 mmHg) 1.3 g was recovered. The yield of 4-chloro-1,3-dioxolan-2-one was about 23%. The recovered 4-chloro-1,3-dioxolan-2-one was subjected to mass spectrometry using a gas-chromatograph-massspectrometer (GC-MS), and the mass (m / z) was 125, and it was confirmed that 4-chloro-1,3-dioxolan-2-one was deuterated. In addition, the mass (m / z) of the non-deuterated 4-chloro-1,3-dioxolan-2-one is 122.

(Example 2)
[Synthesis of deuterated 1,3-dioxol-2-one]
In a nitrogen atmosphere, a flask equipped with a condenser was charged with 1.3 g (10 mmol) of deuterated 4-chloro-1,3-dioxolan-2-one and 1 ml of dehydrated diethyl ether. .3 g (12 mmol) was added, and dehydrochlorination was performed by stirring at 50 ° C. for 13 hours. Subsequently, 10 ml of diethyl ether and 10 ml of hexane were added and the stirred solution was filtered to remove the by-produced ammonium salt. Next, the solution from which the ammonium salt had been removed was concentrated using a rotary evaporator and then distilled under reduced pressure to recover 0.3 g of 1,3-dioxol-2-one. The yield of 1,3-dioxol-2-one was 33%. Further, when the collected 1,3-dioxol-2-one was subjected to mass spectrometry using a gas chromatography mass spectrometer, the mass (m / z) was 88, and 1,3-dioxol-2-one was heavy. It was confirmed that it was hydrogenated. The mass (m / z) of 1,3-dioxol-2-one that is not deuterated is 86.

(Example 3)
[Synthesis of deuterated 4-fluoro-1,3-dioxolan-2-one]
In a flask under nitrogen atmosphere, 1.3 g (10 mmol) of deuterated 4-chloro-1,3-dioxolan-2-one and 0.7 g (12 mmol) of potassium fluoride prepared by spray drying as a fluorinating agent. ) And stirred at 50 ° C. to replace chlorine and fluorine, and extracted with diethyl ether. Subsequently, the extract was washed with saturated brine, dried over sodium sulfate, and distilled under reduced pressure to obtain 0.9 g of 4-fluoro-1,3-dioxolan-2-one (boiling point: 75 ° C./5 mmHg). It was collected. The yield of 4-fluoro-1,3-dioxolan-2-one was 80%. Further, when the collected 4-fluoro-1,3-dioxolan-2-one was subjected to mass spectrometry using a gas chromatograph mass spectrometer, the mass (m / z) was 109, and 4-fluoro-1,3 -It was confirmed that dioxolan-2-one was deuterated. Note that the mass (m / z) of 4-fluoro-1,3-dioxolan-2-one that is not deuterated is 106.

Example 4
[Synthesis of deuterated dimethyl carbonate]
To a diethyl ether solution of 1.5 g (5 mmol) of triphosgene and 1.1 g (30 mmol) of deuterated methanol was added dropwise a diethyl ether solution of 2.4 g (30 mmol) of pyridine as a trapping agent, and after stirring for 7 hours, Extraction with diethyl ether and distillation at atmospheric pressure recovered 0.9 g of dimethyl carbonate. The yield of dimethyl carbonate was 60%. Further, when the collected dimethyl carbonate was subjected to mass spectrometry using a gas chromatograph mass spectrometer, the mass (m / z) was 96, and it was confirmed that dimethyl carbonate was deuterated. In addition, the mass (m / z) of the non-deuterated dimethyl carbonate is 90.

(Example 5)
The secondary battery shown in FIGS. First, lithium carbonate (Li ₂ CO ₃ ) and cobalt carbonate (CoCO ₃ ) are mixed at a molar ratio of Li ₂ CO ₃ : CoCO ₃ = 0.5: 1, and calcined in air at 900 ° C. for 5 hours. A fired product was obtained. When the obtained fired product was subjected to X-ray diffraction measurement, it was in good agreement with the LiCoO ₂ peak registered in the JCPDS file. This LiCoO ₂ was pulverized to obtain a LiCoO ₂ powder having a cumulative 50% particle size of 150 μm obtained by a laser diffraction method, and used as a positive electrode active material. 95 parts by mass of this LiCoO ₂ powder and 5 parts by mass of lithium carbonate are mixed, 91 parts by mass of this mixture, 6 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyvinylidene fluoride as a binder are mixed. After preparing the positive electrode mixture, it was dispersed in N-methyl-2-pyrrolidone as a solvent to obtain a positive electrode mixture slurry. Subsequently, the positive electrode mixture slurry is uniformly applied to both surfaces of a positive electrode current collector 21A made of an aluminum foil having a thickness of 20 μm and dried, followed by compression molding to form a positive electrode active material layer 21B. did. After that, an aluminum positive electrode lead 25 was attached to one end of the positive electrode current collector 21A.

  Further, 90 parts by mass of artificial graphite as a negative electrode active material and 10 parts by mass of polyvinylidene fluoride as a binder were mixed and dispersed in N-methyl-2-pyrrolidone as a solvent to obtain a negative electrode mixture slurry. Subsequently, the negative electrode mixture slurry was uniformly applied to a negative electrode current collector 22A made of a copper foil, dried, and then compression molded to form a negative electrode active material layer 22B, whereby the negative electrode 22 was produced. Subsequently, a negative electrode lead 26 made of nickel was attached to one end of the negative electrode current collector 22A.

  After each of the positive electrode 21 and the negative electrode 22 was prepared, a separator 23 made of a microporous polypropylene film having a thickness of 25 μm was prepared, and the negative electrode 22, the separator 23, the positive electrode 21, and the separator 23 were stacked in this order to form a spiral structure. By winding many times, a spiral wound electrode body 20 having an outer diameter of 18 mm was produced.

After producing the wound electrode body 20, the wound electrode body 20 is sandwiched between the pair of insulating plates 12 and 13, the negative electrode lead 26 is welded to the battery can 11, and the positive electrode lead 25 is welded to the safety valve mechanism 15. The wound electrode body 20 was housed inside a nickel-plated iron battery can 11. Subsequently, an electrolytic solution was injected into the battery can 11 by a reduced pressure method. The electrolyte includes 1,3-dioxolan-2-one, dimethyl carbonate, and deuterated 1,3-dioxol-2-one, 1,3-dioxolan-2-one: dimethyl carbonate: heavy A solution obtained by dissolving LiPF ₆ as an electrolyte salt in a mixed solvent in which hydrogenated 1,3-dioxol-2-one = 47.5: 47.5: 5 was mixed was used. The concentration of LiPF _{6 in} the electrolytic solution was 1 mol / l.

  After that, the battery lid 24 was caulked to the battery can 21 via the gasket 27 to produce a cylindrical secondary battery having a diameter of 18 mm and a height of 65 mm.

  As Comparative Example 5 with respect to Example 5, a secondary battery was fabricated in the same manner as Example 5 except that deuterated 1,3-dioxol-2-one was not used.

  The cycle characteristics of the fabricated secondary batteries of Example 5 and Comparative Example 5 were examined. The cycle characteristics are: 50 cycles of charge / discharge at 23 ° C., 50th cycle discharge capacity maintenance ratio (50th cycle discharge capacity / first cycle discharge capacity) × 100 (%) with respect to the first cycle discharge capacity. Asked. At that time, charging is performed until the battery voltage reaches 4.2 V at a constant current of 1.1 A, and then is performed until the current value reaches 20 mA at a constant voltage of 4.2 V, and discharging is performed at a constant current density of 2 A. This was done until the battery voltage reached 3.0V. The results are shown in Table 1.

  As can be seen from Table 1, even when deuterated 1,3-dioxol-2-one is used, cycle characteristics are similar to those when undeuterated 1,3-dioxol-2-one is used. It has been found that it can be improved.

  Moreover, when the secondary battery of Example 5 was disassembled and the coating on the negative electrode surface was analyzed by TOF-SIMS (Time Of Fright-Secondary Ion Mass Spectroscopy), the number of carbon atoms was 3 or more. Of deuterated hydrocarbons and deuterated alkoxylithium were confirmed. That is, the decomposition behavior of 1,3-dioxol-2-one could be clarified. In addition, the amount of 1,3-dioxol-2-one added and the charging conditions could be clarified by examining the amount of the coating containing deuteride in the coating.

  Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the embodiments and examples, and various modifications can be made. For example, in the above embodiments and examples, the case where an electrolytic solution is used as the electrolyte has been described. However, the electrolytic solution may be held in a polymer compound to form a gel electrolyte.

  In the above embodiments and examples, a secondary battery using lithium as an electrode reactant has been described. However, other alkali metals such as sodium (Na) or potassium (K), magnesium or calcium (Ca), or the like. The present invention can also be applied to the case of using other light metals such as alkaline earth metals or aluminum. In addition, the present invention can be applied to a secondary battery that uses a lithium dissolution precipitation reaction in the negative electrode.

  Furthermore, in the above-described embodiment or example, a cylindrical secondary battery has been specifically described, but the present invention has other shapes such as a laminate film type, a coin type, a button type, a square type, or a large size. The present invention can be similarly applied to secondary batteries having other structures or secondary batteries having other structures such as a stacked structure. Further, the present invention is not limited to the secondary battery, and can be similarly applied to other batteries such as a primary battery.

  In addition, although the case where the carbonate ester compound is used for a battery has been described in the above embodiment or example, it can also be used for a capacitor or the like.

It is sectional drawing showing the structure of the secondary battery using the carbonate ester compound of this invention. It is sectional drawing which expands and represents a part of winding electrode body in the secondary battery shown in FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Battery can, 12, 13 ... Insulation board, 14 ... Battery cover, 15 ... Safety valve mechanism, 15A ... Disc board, 16 ... Heat sensitive resistance element, 17 ... Gasket, 20 ... Winding electrode body, 21 ... Positive electrode, 21A DESCRIPTION OF SYMBOLS ... Positive electrode collector, 21B ... Positive electrode active material layer, 22 ... Negative electrode, 22A ... Negative electrode collector, 22B ... Negative electrode active material layer, 23 ... Separator, 24 ... Center pin, 25 ... Positive electrode lead, 26 ... Negative electrode lead.

Claims (14)

A carbonate ester compound, wherein at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O or ¹⁸ O.   2. The carbonic acid ester compound according to claim 1, which is at least one member selected from the group consisting of a chain compound, a cyclic compound, and an unsaturated compound. The carbonic acid ester compound according to claim 1, which is at least one member selected from the group consisting of the compounds represented by Chemical formula 1 or Chemical formula 2.

(Wherein, R1, R2 represents a hydrocarbon group or at least a portion of the hydrogen is replaced by halogen groups. However, at least some of the constituent elements, deuterium, ¹³ C, ¹⁷ O or ¹⁸ O.)

(In the formula, R3 represents a hydrocarbon group having a single bond between carbons or a double bond between carbons or a group in which at least a part of hydrogen is substituted with halogen, provided that at least a part of the constituent elements. Is deuterium, ¹³ C, ¹⁷ O or ¹⁸ O.) At least one member selected from the group consisting of alcohols containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O, and phosgene, triphosgene, halogenated formate, carbonate and halogenated carbonate as at least a part of the constituent elements. A method for producing a carbonate compound comprising a step of reacting with a seed. A method for producing a carbonic acid ester compound, comprising a step of reacting an alkylene oxide containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O with at least a part of constituent elements and carbon dioxide. A method for producing a carbonic acid ester compound, comprising a step of halogenating a carbonic acid ester containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O in at least a part of constituent elements with a halogenating agent. It includes a step of substituting halogen of a halogenated carbonate containing deuterium, ¹³ C, ¹⁷ O or ¹⁸ O with another halogen by halogen exchange reaction at least in part of the constituent elements. A method for producing a carbonate compound. A step of forming an unsaturated bond by dehydrohalogenating a halogenated carbonate containing deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O as a constituent element at least in part using a base. A method for producing a carbonic acid ester compound. An electrolyte comprising a carbonate ester compound in which at least a part of constituent elements is deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O.   The electrolyte according to claim 9, wherein the carbonate compound includes at least one selected from the group consisting of a chain compound, a cyclic compound, and an unsaturated compound. 10. The electrolyte according to claim 9, wherein the carbonate compound includes at least one selected from the group consisting of the compounds shown in Chemical Formula 3 or Chemical Formula 4.

(In the formula, R 1 and R 2 represent a hydrocarbon group or a group in which at least a part of hydrogen is substituted with a halogen. However, at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O or ¹⁸ O.)

(In the formula, R3 represents a hydrocarbon group having a single bond between carbons or a double bond between carbons or a group in which at least a part of hydrogen is substituted with halogen, provided that at least a part of the constituent elements. Is deuterium, ¹³ C, ¹⁷ O or ¹⁸ O.) A battery comprising an electrolyte together with a positive electrode and a negative electrode,
The battery includes a carbonate ester compound in which at least a part of constituent elements is deuterium, ¹³ C, ¹⁷ O, or ¹⁸ O.   The battery according to claim 12, wherein the carbonate compound includes at least one selected from the group consisting of a chain compound, a cyclic compound, and an unsaturated compound. The battery according to claim 12, wherein the carbonate compound includes at least one selected from the group consisting of the compounds shown in Chemical Formula 5 or Chemical Formula 6.

(In the formula, R 1 and R 2 represent a hydrocarbon group or a group in which at least a part of hydrogen is substituted with a halogen. However, at least a part of the constituent elements is deuterium, ¹³ C, ¹⁷ O or ¹⁸ O.)

(In the formula, R3 represents a hydrocarbon group having a single bond between carbons or a double bond between carbons or a group in which at least a part of hydrogen is substituted with halogen, provided that at least a part of the constituent elements. it is deuterium, a ¹³ C, ¹⁷ O or ¹⁸ O.)

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