JP4868350B2 - Non-aqueous electrolyte battery - Google Patents

Description

  The present invention relates to a nonaqueous electrolyte battery, and more particularly to a nonaqueous electrolyte battery using a nonaqueous electrolyte composed of a lithium salt, an ionic liquid, and an organic solvent.

  In recent years, non-aqueous electrolyte batteries typified by lithium-ion batteries have attracted attention as power supplies for electronic equipment, power storage power supplies, power supplies for electric vehicles, and the like that have been improved in performance and size.

  These non-aqueous electrolyte batteries generally use a non-aqueous electrolyte (non-aqueous electrolyte) that is liquid at room temperature. The non-aqueous electrolyte is generally obtained by dissolving a lithium salt that is solid at room temperature in an organic solvent that is liquid at room temperature. Examples of the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl. Organic solvents such as carbonate, methyl ethyl carbonate, γ-butyrolactone, propiolactone, valerolactone, tetrahydrofuran, dimethoxyethane, diethoxyethane, methoxyethoxyethane and the like are used.

On the other hand, it has been proposed to use an ionic liquid that is liquid at room temperature as a non-aqueous electrolyte for a non-aqueous electrolyte battery. The ionic liquid itself is liquid at room temperature but is substantially non-volatile and has high flame retardancy. Among non-aqueous electrolytes, the use of non-aqueous electrolytes that have characteristics such as no risk of ignition is desired, particularly for relatively large non-aqueous electrolyte applications such as power storage power sources and electric vehicle power sources. The technique using the ionic liquid as an electrolyte has attracted attention (for example, see Patent Documents 1 to 3).
JP 2001-319688 A Japanese Patent No. 2981545 JP 2003-331918 A

For example, Patent Document 1 uses an ionic liquid composed of a cyclic quaternary ammonium organic cation having an aromatic ring typified by 1-ethyl-3-methylimidazolium cation and a non-aqueous electrolyte containing a lithium salt. A battery using a negative electrode active material, such as lithium titanium oxide, in which the operating potential is nobler than 1 V with respect to the potential of metallic lithium has been proposed. According to this technique, since the electrolyte is flame retardant, it is possible to obtain a battery that is particularly suitable for applications that require a high level of safety. However, when an ionic liquid composed of a cyclic quaternary ammonium organic cation having an aromatic ring typified by an imidazolium cation is used as a non-aqueous electrolyte, the non-aqueous electrolyte is 1 V (vs Li ^/ Li ⁺ ) It is easily decomposed at the following potential, and when the negative electrode is operated at 1 V (vs. Li ^/ Li ⁺ ) or less, the battery performance is extremely inferior. Therefore, as described in the same document, it is necessary to use a negative electrode active material such as Li _4/3 Ti _5/3 O ₄ whose operating potential is nobler than 1 V with respect to the potential of metallic lithium. there were. Therefore, when a negative electrode active material that operates at a potential of 1 V (vs. Li ^/ Li ⁺ ) or less, such as a carbonaceous material, is used for the negative electrode, a battery with good performance cannot be obtained. There was a problem that it could not be obtained.

On the other hand, Patent Document 2 proposes a battery using a non-aqueous electrolyte containing an ionic liquid composed of an aliphatic quaternary ammonium organic cation typified by a trimethylhexylammonium cation. Further, Patent Document 3 includes N-methyl-N-ethylpyrrolidinium cation, N-methyl-N-propylpyrrolidinium cation, N-methyl-N-ethylpiperidinium cation, and N-methyl-N- A battery using an ionic liquid composed of an aliphatic cyclic quaternary ammonium organic cation such as propylpiperidinium cation and a non-aqueous electrolyte containing a lithium salt and using metallic lithium as a negative electrode active material has been proposed. According to these techniques, since the resistance to anion reduction is superior to the case where an ionic liquid composed of a cyclic quaternary ammonium organic cation having an aromatic ring is used as a nonaqueous electrolyte, Such a negative electrode active material that operates at a potential of 1 V (vs. Li ^/ Li ⁺ ) or less can be used for the negative electrode. However, when a carbonaceous material, particularly graphite, is used for the negative electrode in a nonaqueous electrolyte battery made of these ionic liquids, there is a problem that the battery performance is remarkably inferior. This is presumed to be due to side reactions such as reductive decomposition and co-insertion of quaternary ammonium organic cation peculiar when a carbonaceous material is used for the negative electrode.

  Furthermore, since the ionic liquids shown in these patent documents have a higher melting point and higher viscosity than general non-aqueous electrolytes, the mobility of carrier ions such as lithium ions is sufficient. However, there is a problem that it cannot be made high. Therefore, a non-aqueous electrolyte battery using a non-aqueous electrolyte made of an ionic liquid has a problem that high rate charge / discharge characteristics are not sufficient as compared with a non-aqueous electrolyte battery using a general non-aqueous electrolyte.

In contrast, attempts have been proposed to improve high rate charge / discharge characteristics by using a non-aqueous electrolyte containing an ionic liquid and an organic solvent at the same time (see, for example, Patent Documents 4 to 6).
JP 11-260400 A JP 2004-303642 A JP 2003-288939 A

For example, in Patent Document 4, LiBF ₄ is added to 1-methyl-3-ethylimidazolium tetrafluoroborate (EMIBF ₄ ) so that the lithium ion content in the molten salt is 0.5 mol / kg. Furthermore, a battery using an ionic liquid to which 1% by volume of ethylene carbonate EC is added is described (see paragraph 0040). In the same document, “the room temperature type molten salt contains at least one of the cyclic carbonate and the chain carbonate. This carbonate is reduced and decomposed during initial charge and discharge to form carbonate ions (CO ₃ ^2- ) and CO ₃ ^2- reacts with Li to form a protective film on the surface of the negative electrode. Since the protective film can be appropriately formed on the negative electrode surface, reductive decomposition of the nonaqueous electrolyte by the negative electrode can be suppressed, charge / discharge efficiency can be improved, and cycle life can be greatly improved. In addition, since the viscosity and freezing point of the nonaqueous electrolyte can be lowered at the same time, the large current characteristics and the low temperature characteristics can be improved. " As the optimum amount of the organic solvent that can be effectively exerted, “If the carbonate content is less than 0.1% by volume, the effect of forming the protective film is small, so that it is difficult to improve the cycle life. On the other hand, if the carbonate content exceeds 30% by volume, the flash point and thermal stability of the non-aqueous electrolyte are significantly reduced, and a more preferable range of the carbonate content is 1 to 5% by volume. , Cyclic carbonate is preferred "(see paragraph 0026). However, as quaternary ammonium cations, dialkylimidazolium ions (DI ⁺ ), imidazolium ions such as trialkylimidazolium ions (TI ⁺ ), tetraalkylammonium ions (TA ⁺ ), and alkylpyridinium ions (AP ⁺ ). Etc. (see paragraph 0028) are not mentioned, but the use of saturated aliphatic cyclic quaternary ammonium cations is not described.

For example, Patent Document 5, 1-ethyl-3-methylimidazolium cation (EMI ⁺⁾ and _{N (CF 3 SO 2) 2} - in the ionic liquid consisting of an anion (EMITFSI) 1 liter 1 mol of LiN (CF A battery using a non-aqueous electrolyte in which ₃ SO ₂ ) ₂ is dissolved and 10% by mass of ethylene carbonate is mixed is described (see paragraph 0066). In addition, the same document states that “the electrolyte of the battery of the present invention may further contain an organic solvent as used in a general lithium ion battery. At this time, the organic solvent has a dielectric constant of 35 or more. It is preferable to select and use one, because the effect of the present invention can be exhibited more effectively ”(see paragraph 0020). However, as the quaternary ammonium organic cation, a cyclic quaternary ammonium cation having an aromatic ring consisting of a 5-membered ring or a 6-membered ring is used (Claim 1), and a specific effect is obtained. There is no description about the optimal amount of organic solvent to be mixed.

For example, Patent Document 6 discloses a mixed solvent in which bistrifluoromethylsulfonylimide trimethyloctyl ammonium (TMOATFSI), ethylene carbonate (EC), and diethyl carbonate (DEC) are mixed at a volume ratio of 15:15:70. In addition, a battery using a non-aqueous electrolyte in which 0.5 mol / l of LiN (CF ₃ SO ₂ ) ₂ and LiPF ₆ and 1 mol / l of LiPF ₆ are dissolved, and metal lithium as a negative electrode active material is used. (See paragraph 0024). In addition, the same document states that “the non-aqueous solvent in the non-aqueous electrolyte solution includes a room temperature molten salt (synonymous with the ionic liquid in the present invention) and carbonate. In addition, since the non-aqueous solvent contains 50% by volume or more of carbonate, the viscosity of the non-aqueous electrolyte decreases, and the ionic conductivity of the non-aqueous electrolyte increases. In particular, in order to improve safety and improve the ionic conductivity of the non-aqueous electrolyte to improve the charge / discharge characteristics, the non-aqueous system described above is used. There is a description that "the carbonate is preferably contained in the solvent in the range of 50 to 90% by volume, more preferably 70 to 85% by volume" (see paragraph 0009). However, it is only described that tetraalkyl quaternary ammonium salt is used as the ionic liquid (see paragraph 0011), and also the flame retardancy effect by using the ionic liquid and the use of carbonate. There is no description about the improvement effect of a high rate charge / discharge characteristic.

Furthermore, a nonaqueous electrolyte battery using a nonaqueous electrolyte that uses an ionic liquid and that does not substantially contain an organic solvent and a carbonaceous material typified by graphite as a negative electrode active material has also been proposed (for example, Patent Documents 7 to 9 and Non-Patent Documents 1 to 3). However, in all of these proposals, a non-aqueous electrolyte battery using a non-aqueous electrolyte made of an ionic liquid does not have sufficient high rate charge / discharge characteristics compared to a non-aqueous electrolyte battery using a general non-aqueous electrolyte. This problem was not solved.
JP 2002-373704 A JP-A-2005-26091 JP 2005-44685 A M. Holzapfel, C. Jost, and P. Novak, Chemistry Communications, 2098 ・ 9 (2004) Yasushi Katayama, Makoto Yukumoto, and Takashi Miura, Electrochemical and Solid-State Letters, 6 (5) A96-A97 (2003) Study Group for Molten Salt / Thermal Technology "Basics of Molten Salt / Thermal Technology", Agne Technology Center, 1993, 313p (ISBN 4-900041-24-6)

  The present invention has been made in view of the above problems, and ensures high safety (flame retardancy) obtained by using an ionic liquid for a non-aqueous electrolyte, has a high energy density, and has a high rate. It is an object of the present invention to provide a nonaqueous electrolyte battery having excellent charge / discharge characteristics.

  The configuration of the present invention for solving the above problems is as follows. However, the action mechanism includes estimation, and the success or failure of the action mechanism does not limit the present invention.

In addition, the ionic liquid as used in this application means the ionic compound which at least one part exhibits liquid state at normal temperature. The normal temperature is a temperature range in which an electrochemical device using the normal operation is assumed to normally operate. The upper limit is about 100 ° C., in some cases about 60 ° C., and the lower limit is about −50 ° C., in some cases −20 It is about ℃. On the other hand, the inorganic molten salt such as Li ₂ CO ₃ —Na ₂ CO ₃ —K ₂ CO ₃ used for various electrodepositions as described in Non-Patent Document 3 has a melting point of 300 ° C. or higher. However, it does not exhibit a liquid form within the temperature range in which the electrochemical device is normally assumed to operate, and is not included in the ionic liquid in the present invention.

The present invention provides a nonaqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte composed of at least a lithium salt and a liquid organic compound at room temperature, as described in claim 1. The nonaqueous electrolyte is an ionic liquid composed of at least a saturated aliphatic cyclic quaternary ammonium cation and an anion composed only of a nonmetallic element, and a cyclic carbonate and / or a chain carbonate as the “organic compound liquid at normal temperature”. contain, and all SANYO containing lithium cations in a concentration of more than _{0.5mol / l, n (C n} F 2 n + 1 SO 2) having a perfluoroalkyl group ₂ ^- (n = _1~4) If, PF ₆ having no perfluoroalkyl group ^- Rukoto to contain both (but non prepared by dissolving an electrolyte in a mixed solvent of an organic solvent and ionic liquid A electrolytic solution as the electrolyte, those using a salt of the anion compound represented by LiPF ₆ and the following general formula (1)
{However, M is a transition metal, a group III, IV or V element of the periodic table, b is 1 to 3, m is 1 to 4, n is 0 to 8, q is 0 or 1 respectively. , R ¹ is C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ halogenated alkylene, C ₆ -C ₂₀ arylene, or C ₆ -C ₂₀ halogenated arylene (the alkylene and arylene have the structure) And R ¹ may be bonded to each other.), R ² is halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ Alkyl halides, C ₆ -C ₂₀ aryls, C ₆ -C ₂₀ aryl halides, or X ³ R ³ (these alkyls and aryls may have substituents, heteroatoms in their structures, the n number R ² each may combine with each other to form a ring present.), X ^{1, 2,} X ³ is O, S, or NR ^4, R ^3, R ⁴ are, each independently, hydrogen, alkyl of C ₁ -C _10, alkyl halide C ₁ ~C _10, C ₆ ~C ₂₀ aryls and C ₆ -C ₂₀ aryl halides are shown respectively. (These alkyls and aryls may have a substituent or a hetero atom in the structure, and a plurality of R ³ and R ⁴ are respectively present. May combine to form a ring. }, And a mixed solvent obtained by mixing N-methyl-N′-propylpiperidinium bis (trifluoromethanesulfonyl) imide, ethylene carbonate and diethyl carbonate in a volume ratio of 20:30:50, LiPF ₆ as an electrolyte Excluding non-aqueous electrolyte solution only dissolved. ) .

  According to such a configuration, it is surprisingly surprising that the non-aqueous electrolyte exhibits flame retardancy while containing a large amount of flammable cyclic carbonate and / or chain carbonate, and at the same time has low viscosity and high ionic conductivity. Therefore, the present invention has been found to provide a nonaqueous electrolyte battery that ensures high safety, has a high energy density, and is excellent in high rate charge / discharge characteristics. It came to.

  That is, the non-aqueous electrolyte of the present invention contains an ionic liquid formed by a saturated aliphatic cyclic quaternary ammonium cation and an anion consisting only of a non-metallic element as an “organic compound that is liquid at room temperature”. At the same time, even if the non-aqueous electrolyte contains a large amount of flammable cyclic carbonate and / or chain carbonate, it is liquid at room temperature but has substantially no volatility, so it has high nonflammability. Therefore, a non-aqueous electrolyte that exhibits flame retardancy can be obtained. On the other hand, the non-aqueous electrolyte of the present invention contains a large amount of high viscosity and high melting point ionic liquid by containing cyclic carbonate and / or chain carbonate as “organic compound liquid at normal temperature”. However, since the low-viscosity and low-boiling point characteristics of the cyclic carbonate and / or chain carbonate that can make the mobility of carrier ions such as lithium ions sufficiently high can be utilized, A non-aqueous electrolyte having high ionic conductivity can be provided. As a result, the nonaqueous electrolyte battery according to the present invention can be a nonaqueous electrolyte battery that ensures high safety, has a high energy density, and is excellent in high rate charge / discharge characteristics.

  Further, since the non-aqueous electrolyte contains lithium cations at a concentration of 0.5 mol / l or more, two or more types of cations having greatly different ion sizes such as lithium cations and quaternary ammonium cations coexist. It is estimated that the mobility of carrier ions can be kept high by suppressing the crystallization of the non-aqueous electrolyte at the molecular level because the arrangement of ions constituting the ionic liquid tends to be highly amorphous. Is done.

  Further, it should be noted that an ionic liquid formed by a saturated aliphatic cyclic quaternary ammonium cation and an anion consisting only of a nonmetallic element, and a negative carbonate by containing both cyclic carbonate and / or chain carbonate Even when a carbonaceous material, particularly graphite, is used as the negative electrode active material used in the present invention, a non-aqueous electrolyte battery can be provided without significantly inferior battery performance. The reason why the above effect is exhibited is not necessarily clear, but the coexistence of cyclic carbonate and / or chain carbonate suppresses side reactions such as reductive decomposition and co-insertion of saturated aliphatic cyclic quaternary ammonium cations. It is estimated that.

  Moreover, as described in claim 2, the present invention is characterized in that the “organic compound that is liquid at normal temperature” contains an ionic liquid in an amount of 30 mass percent or more and less than 70 mass percent.

  Furthermore, as described in claim 3, the present invention is characterized in that the "organic compound that is liquid at normal temperature" contains cyclic carbonate and / or chain carbonate more than 30 mass percent and 70 mass percent or less. Yes.

  According to such a configuration, it becomes easy to set the melting point and the viscosity low while imparting flame retardancy to the non-aqueous electrolyte, and thus the above-described action can be effectively obtained.

Further, according to the present invention, as described in claim 5, the “anion comprising only a nonmetallic element” constituting the lithium salt and the ionic liquid is PF ₆ ⁻ and N (C _n F _{2n + 1} SO ₂ ). It is characterized in that it is at least one kind of anions selected from ₂ ⁻ (n = 1 to 4).

Furthermore, as described in claim 1, the present invention contains both PF ₆ ⁻ and N (C _n F _{2n + 1} SO ₂ ) ₂ ⁻ (n = 1 to 4) , so that it is solid at room temperature. Even in the state where a certain lithium salt coexists, it becomes easy for the non-aqueous electrolyte to maintain a good liquid state, and the above action can be effectively obtained.

Moreover, this invention is characterized by the negative electrode active material used for the said negative electrode being a carbonaceous material, as described in Claim 5 .

According to such a configuration, since the operating potential of the negative electrode can be set in the vicinity of 0 V (vs. Li ^/ Li ⁺ ), a high energy density that takes advantage of the excellent effects given by the physical properties of the nonaqueous electrolyte as described above. It is possible to easily provide a nonaqueous electrolyte battery having excellent electrochemical characteristics.

  According to the present invention, there is provided a nonaqueous electrolyte battery having high energy density and excellent high rate charge / discharge characteristics while ensuring high safety obtained by using an ionic liquid for a nonaqueous electrolyte. Can do.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these descriptions.

  The ionic liquid in the present invention has a saturated aliphatic cyclic quaternary ammonium cation. Examples of the saturated aliphatic cyclic quaternary ammonium cation include a pyrrolidinium cation and a piperidinium cation.

  Examples of the pyrrolidinium cation include N, N-dimethylpyrrolidinium cation, N, N-diethylpyrrolidinium cation, N-methyl-N-ethylpyrrolidinium cation, and N-methyl-N-propylpyrrolidinium. Examples thereof include, but are not limited to, a cation, an N-methyl-N-butylpyrrolidinium cation, and an N-methyl-N-hexylpyrrolidinium cation.

  Examples of the piperidinium cation include N, N-dimethylpiperidinium cation, N, N-diethylpiperidinium cation, N-methyl-N-ethylpiperidinium cation, and N-methyl-N-propylpiperidinium. Examples include, but are not limited to, a cation, an N-methyl-N-butylpiperidinium cation, and an N-methyl-N-hexylpiperidinium cation.

  Among them, N-methyl-N-ethylpiperidinium cation, N-methyl-N-propylpiperidinium cation, N-methyl-N-butylpiperidinium cation, N-methyl-N-hexylpiperidinium cation It is preferable that at least one of the cations selected from In addition, the ionic liquid which has these saturated aliphatic cyclic | annular quaternary ammonium cations may be used independently, and may be used in mixture of 2 or more types.

The anion consisting only of the non-metallic elements constituting the ionic liquid and lithium salt in the present invention is not particularly limited, but ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CN ⁻ , COO ⁻ , SO ₂ CF ₂ −, N (CF ₃ SO ₂ ) ₂ ⁻ , N (C ₂ F ₅ SO ₂ ) ₂ ⁻ , N (CF ₃ SO ₂ ) (C ₂ F ₅ SO ₂ ) ⁻ N (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) ⁻ , C (CF ₃ SO ₂ ) ₃ ⁻ , C (C ₂ F ₅ SO ₂ ) ₃ ^{− and the} like. Among them, PF ₆ ^- and _{N (C n F 2n + 1} SO 2) 2 - (n = 1~4) of anion selected from, is preferably at least one.

  In addition, the anion which consists only of these nonmetallic elements may be used independently, and may be used in mixture of 2 or more types. When two or more kinds of anions are contained, an ionic liquid having two or more kinds of anions and a lithium salt comprising one kind of anions may be mixed, and two or more kinds of lithium salts having different anions may be mixed with one kind of anion. An ionic liquid may be mixed, and further, an ionic liquid having a different anion species and a lithium salt may be mixed.

In particular, by containing N (C _n F _{2n + 1} SO ₂ ) ₂ ⁻ (n = 1 to 4) having a perfluoroalkyl group and PF ₆ ⁻ having no perfluoroalkyl group, a low melting point and a low melting point are obtained. High flame retardancy can be realized at the same time as developing the viscosity. In addition, since two or more types of anions coexist, the arrangement of ions constituting the ionic liquid tends to be highly amorphous. Therefore, crystallization at the molecular level of the nonaqueous electrolyte is suppressed, and carrier ions It is estimated that the mobility can be kept high. It should be noted that N (C _n F _{2n + 1} SO ₂ ) ₂ ⁻ (n = 1 to 4) having a perfluoroalkyl group is generally a relatively low potential (for example, N ( CF ₃ SO ₂ ) ₂ ⁻ is 3.8 V (vs. Li ^/ Li ⁺ )), and the phenomenon of corroding aluminum used in the positive electrode current collector of the nonaqueous electrolyte battery is known. By containing N (C _n F _{2n + 1} SO ₂ ) ₂ ⁻ (n = 1 to 4) having a perfluoroalkyl group and PF ₆ ⁻ having no perfluoroalkyl group, the nonaqueous electrolyte can be converted into a cyclic carbonate. And even if it contains a large amount of chain carbonate, such a phenomenon does not occur. As a result, since it becomes easy to set the melting point and viscosity of the nonaqueous electrolyte lower, the electrochemical characteristics of the nonaqueous electrolyte can be made excellent, and the nonaqueous electrolyte battery according to the present invention has high safety. It is possible to obtain a non-aqueous electrolyte battery having high energy density and excellent high rate charge / discharge characteristics.

  The non-aqueous electrolyte of the present invention is an organic compound that is liquid at room temperature, cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and / or dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc. The chain carbonate is contained. As other organic compounds that can be added at room temperature, organic solvents generally used for electrolytes for lithium secondary batteries can be used. Specifically, γ-butyrolactone, propiolactone, valerolactone can be used. , Tetrahydrofuran, dimethoxyethane, diethoxyethane, methoxyethoxyethane and the like, but are not particularly limited thereto. These may be used alone or in combination of two or more.

  The ionic liquid and other organic compounds that are liquid at normal temperature can be mixed at an arbitrary mixing ratio, but in view of the compatibility of the non-aqueous electrolyte with flame retardancy and electrochemical characteristics, The ionic liquid is desirably contained in the range of 30 to 70% by weight and cyclic carbonate and / or chain carbonate in a range of more than 30% by weight and 70% by weight or less. When the content of the ionic liquid is less than 30 mass percent, the proportion of the organic compound that is flammable by itself becomes too large, and it becomes difficult to express the flame retardancy of the nonaqueous electrolyte. On the contrary, when the content of the cyclic carbonate and / or the chain carbonate is 30% by mass or less, it becomes difficult to set the melting point and the viscosity of the nonaqueous electrolyte low, and it becomes difficult to maintain high ionic conductivity. On the other hand, the non-aqueous electrolyte in the present invention contains the cyclic carbonate and / or the chain carbonate up to a range of 70 mass percent or less, but if the ionic liquid is contained in an amount of 30 mass percent or more, the non-aqueous electrolyte flame retardancy Even if the ionic liquid is contained up to a range of less than 70 mass percent, high ionic conductivity can be maintained if the cyclic carbonate and / or chain carbonate is contained in an amount exceeding 30 mass percent. Become. In the above points, the content of the ionic liquid in the nonaqueous electrolyte is 30 mass percent or more and less than 70 mass percent, and the cyclic carbonate and / or chain carbonate content is more than 30 mass percent and less than 70 mass percent. In particular, the content of the ionic liquid is preferably in the range of 40 mass percent to 60 mass percent, and the cyclic carbonate and / or chain carbonate content is in the range of 40 mass percent to 60 mass percent.

  The lithium cation content in the non-aqueous electrolyte is preferably in the range of 0.5 to 3 mol / l. When the content of the lithium salt is less than 0.5 mol / l, the electrolyte resistance is too high, and the charge / discharge efficiency of the battery is lowered. On the contrary, if the content of the lithium salt exceeds 3 mol / l, the melting point of the nonaqueous electrolyte rises, and it becomes difficult to maintain a liquid state at room temperature. In view of the above, the content of the lithium salt in the non-aqueous electrolyte is preferably in the range of 0.5 to 3 mol / l, more specifically in the range of 0.5 to 2 mol / l.

  Examples of the negative electrode active material that is a main component of the negative electrode of the nonaqueous electrolyte battery in the present invention include a carbonaceous material and a material that is modified by adding phosphorus or boron for the purpose of improving the negative electrode characteristics. . Among carbonaceous materials, graphite has a working potential very close to that of metallic lithium. Therefore, when lithium salt is used as an electrolyte salt, self-discharge can be reduced, and irreversible capacity in charge / discharge can be reduced, which is preferable as a negative electrode active material. . Graphite crystals include the well-known hexagonal system and others belonging to the rhombohedral system. In particular, rhombohedral graphite has a wide selectivity for a solvent in an electrolytic solution. Even when it is used as a constituent material of an electrolyte, it is desirable because delamination is suppressed and excellent charge / discharge efficiency is exhibited.

The analysis results by X-ray diffraction etc. of rhombohedral graphite that can be suitably used are shown below;
Lattice constant a0 = 0.3635 nm, α = 39.49 °
Most natural graphite and artificial graphite are hexagonal, but it is known that a few percent of rhombohedral structures exist in natural graphite and artificial graphite heat-treated at a very high temperature. It is also known that there is an increase from hexagonal to rhombohedral by grinding or grinding. In particular, graphite having a large amount of rhombohedral system on the surface of the graphite particle and a large amount of hexagonal system inside the particle is most desirable in terms of advantages such as high capacity, solvent resistance, and manufacturing process.

Here, the calculation method of the rhombohedral system contained in the entire graphite crystal described in JP-A-2000-348727 is shown. The peak area of the (101) diffraction line attributed to the rhombohedral crystal measured by the X-ray wide angle diffraction method is represented by r (101), and the peak area of the (101) diffraction line attributed to the hexagonal crystal measured in the same manner. It is assumed that h (101) is used, and the ratio R% of the rhombohedral crystal occupying the entire graphite crystal is calculated by (Equation 1).
(Formula 1) R = [r (101) × 12/15] / [r (101) × 15/12 + h (101)] × 100
Since rhombohedral graphite is desirably contained in an amount of 5% or more of the negative electrode carbonaceous material because of the effect of greatly reducing the irreversible capacity in the initial charge / discharge, 15% is required to obtain a more remarkable effect. It is desirable to include the above.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these descriptions.

(Comparative electrolyte 1)
By mixing 0.4 mol of LiN (CF ₃ SO ₂ ) ₂ (LiTFSI) with 1 liter of N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13-TFSI), a non-aqueous electrolyte Got.

(Comparative electrolyte 2)
1 mol of LiPF ₆ is mixed with 1 liter of a mixed solvent (hereinafter referred to as mixed solvent A) in which ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (MEC) are mixed at a volume ratio of 1: 1: 1. As a result, a non-aqueous electrolyte was obtained.

(Invention electrolyte 1)
25 g of PP13-TFSI and 75 g of the mixed solvent A were mixed, and further LiPF ₆ was mixed so as to be 1 mol / liter to obtain a nonaqueous electrolyte.

(Invention electrolyte 2)
30 g of PP13-TFSI and 70 g of the mixed solvent A were mixed, and further LiPF ₆ was mixed so as to be 1 mol / liter to obtain a nonaqueous electrolyte.

(Invention electrolyte 3)
50 g of PP13-TFSI and 50 g of mixed solvent A were mixed, and further LiPF ₆ was mixed so as to be 1 mol / liter to obtain a nonaqueous electrolyte.

(Invention electrolyte 4)
70 g of PP13-TFSI and 30 g of mixed solvent A were mixed, and further LiPF ₆ was mixed so as to be 1 mol / liter to obtain a nonaqueous electrolyte.

(Invention electrolyte 5)
A nonaqueous electrolyte was obtained by mixing 75 g of PP13-TFSI and 25 g of mixed solvent A, and further mixing LiPF ₆ so as to be 1 mol / liter.

(Invention electrolyte 6)
By mixing 50 g of N-methyl-N-propylpiperidinium tetrafluoroborate (PP13-BF ₄ ) and 50 g of the mixed solvent A, and further mixing LiBF ₄ to be 1 mol / liter, A water electrolyte was obtained.

(Electrolyte flammability test)
An electrolyte flammability test was performed on the above-described electrolytes 1 to 6 and comparative electrolytes 1 and 2. A glass filter was impregnated with each electrolyte, and the presence of ignition / combustion was confirmed by bringing the fire of an alcohol lamp closer to 10 seconds.

(Preparation of non-aqueous electrolyte battery)
A non-aqueous electrolyte battery was produced using the electrolytes 1 to 6 of the present invention and the comparative electrolytes 1 and 2. Let this be the present invention batteries 1-6 and comparative batteries 1-2. A cross-sectional view of the nonaqueous electrolyte battery according to the example is shown in FIG. The non-aqueous electrolyte battery according to the example is composed of a pole group 4 including a positive electrode 1, a negative electrode 2, and a separator 3, a non-aqueous electrolyte, and a metal resin composite film 5 as an exterior material. The positive electrode 1 is formed by applying a positive electrode mixture 11 on a positive electrode current collector 12. The negative electrode 2 is formed by applying a negative electrode mixture 21 on a negative electrode current collector 22. The nonaqueous electrolyte is impregnated in the pole group 4. The metal resin composite film 5 covers the pole group 4 and is sealed on all four sides by heat welding.

Next, a method for manufacturing the nonaqueous electrolyte battery having the above configuration will be described. The positive electrode 1 was obtained as follows. First, LiCoO ₂ and acetylene black, which is a conductive agent, are mixed, and further, a N-methyl-2-pyrrolidone solution of polyvinylidene fluoride is mixed as a binder, and this mixture is used as a positive electrode current collector 12 made of an aluminum foil. After coating on one side, it was dried and pressed so that the positive electrode mixture 11 had a predetermined thickness. The positive electrode 1 was obtained by the above process. The negative electrode 2 was obtained as follows. First, graphite as a negative electrode active material and an N-methyl-2-pyrrolidone solution of polyvinylidene fluoride as a binder were mixed, and this mixture was applied to one side of a negative electrode current collector 22 made of copper foil. It dried and it pressed so that the negative mix 21 might become predetermined thickness. The negative electrode 2 was obtained by the above process. As the separator 3, a polyethylene microporous membrane was used. The pole group 4 was configured by facing the positive electrode mixture 11 and the negative electrode mixture 21, placing the separator 3 therebetween, and laminating the positive electrode 1, the separator 3, and the negative electrode 2 in this order. Next, the electrode group 4 was impregnated with the non-aqueous electrolyte by immersing the electrode group 4 in the non-aqueous electrolyte. Furthermore, the pole group 4 was covered with the metal resin composite film 5, and the four sides were sealed by heat welding.

(Initial discharge capacity test)
An initial discharge capacity test was performed on the battery of the present invention and the comparative battery. The test temperature was 20 ° C. The charging was a constant current charging with a current of 2 mA and a final voltage of 4.2 V. The discharge was a constant current discharge with a current of 2 mA and a final voltage of 3.0V. The obtained discharge capacity was defined as the initial discharge capacity. The design capacities of the battery of the present invention and the comparative battery are all 10 mAh.

(High rate discharge test)
A high rate discharge test was performed on the battery of the present invention and the comparative battery. The test temperature was 20 ° C. A battery whose initial capacity was confirmed under the same conditions as the initial discharge capacity test was charged under the same conditions, and then a constant current discharge with a current of 5 mA and a final voltage of 3.0 V was performed. The obtained discharge capacity was defined as a high rate discharge capacity.
The above results are summarized in Table 1.

  As is apparent from Table 1, the comparative battery 2 (containing no ionic liquid) had good initial discharge capacity and high rate discharge capacity, but the electrolyte had combustibility. Comparative battery 1 (containing no carbonate and having a lithium ion concentration of less than 0.5 mol / l) showed flame retardancy in the electrolyte, but the initial discharge capacity and high rate discharge capacity were different from those of other batteries. It turned out to be greatly inferior.

  In contrast, the batteries 1 to 6 of the present invention (containing a specific ionic liquid and carbonate and having a lithium ion concentration of 0.5 mol / l or more) have an initial discharge capacity and a high rate as compared with the comparative battery 1. In addition to the excellent discharge capacity, it was confirmed that the non-aqueous electrolyte battery has both high safety and good battery performance because the electrolyte also exhibits flame retardancy compared to the comparative battery 2. .

  In order to obtain a non-aqueous electrolyte battery having both the flame retardancy of the electrolyte and good battery performance by comparison between the batteries 1 to 5 of the present invention, the non-aqueous electrolyte contains 30 mass percent or more and 70 mass of ionic liquid. It has become clear that it is desirable to contain less than a percent and / or cyclic carbonate and / or chain carbonate in a range of more than 30 percent by weight and not more than 70 percent by weight (Invention batteries 2 and 3).

Further, according to the comparison between the batteries 3 and 6 of the present invention, the anion consisting only of the non-metallic element constituting the lithium salt and the ionic liquid is PF ₆ ⁻ and N (C _n F _{2n + 1} SO ₂ ) ₂ ⁻ (n = It has become clear that at least one of the anions selected from 1-4) is desirable. In the present _{embodiment, N (C n F 2n +} 1 SO 2) 2 - (n = 1~4) as the _{N (CF 3 SO 2) 2} - and has been described as an example, N (C Similar effects can be obtained by using ₂ F ₅ SO ₂ ) ₂ ⁻ , N (C ₄ F ₉ SO ₂ ) ₂ ⁻ , N (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) ⁻ or the like.

  In this example, N-methyl-N-propylpiperidinium cation was used as an example of saturated aliphatic cyclic quaternary ammonium cation. However, other saturated aliphatic cyclic quaternary ammonium organic cations (N -Methyl-N-ethylpiperidinium cation, N-methyl-N-butylpiperidinium cation, N-methyl-N-hexylpiperidinium cation, etc.) can be used to obtain the same effect.

  As is clear from the above results, according to the present invention, the high safety obtained by using the ionic liquid for the non-aqueous electrolyte is ensured, the energy density is high, and the high rate charge / discharge characteristics are excellent. A non-aqueous electrolyte battery can be provided.

It is sectional drawing of the nonaqueous electrolyte battery which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Positive electrode 11 Positive electrode mixture 12 Positive electrode collector 2 Negative electrode 21 Negative electrode mixture 22 Negative electrode collector 3 Separator 4 Electrode group 5 Metal resin composite film

Claims (5)

In a non-aqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte composed of at least a lithium salt and an organic compound that is liquid at room temperature, the non-aqueous electrolyte is the “organic liquid at room temperature”. The compound "contains at least a saturated aliphatic cyclic quaternary ammonium cation and an anion consisting only of a nonmetallic element, and a cyclic carbonate and / or a chain carbonate, and a lithium cation of 0.5 mol / l. all SANYO containing at concentrations _{above, n (C n F 2 n} + 1 SO 2) 2 having a perfluoroalkyl group ^- and (n = 1~4), PF ₆ having no perfluoroalkyl group ^- the Rukoto be contained together (however, a non-aqueous electrolyte prepared by dissolving an electrolyte in a mixed solvent of an organic solvent and an ambient temperature molten salt, as the electrolyte, those using a salt of the anion compound represented by iPF ₆ and the following general formula (1)
{However, M is a transition metal, a group III, IV or V element of the periodic table, b is 1 to 3, m is 1 to 4, n is 0 to 8, q is 0 or 1 respectively. , R ¹ is C ₁ -C ₁₀ alkylene, C ₁ -C ₁₀ halogenated alkylene, C ₆ -C ₂₀ arylene, or C ₆ -C ₂₀ halogenated arylene (the alkylene and arylene have the structure) And R ¹ may be bonded to each other.), R ² is halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ Alkyl halides, C ₆ -C ₂₀ aryls, C ₆ -C ₂₀ aryl halides, or X ³ R ³ (these alkyls and aryls may have substituents, heteroatoms in their structures, the n number R ² each may combine with each other to form a ring present.), X ^{1, 2,} X ³ is O, S, or NR ^4, R ^3, R ⁴ are, each independently, hydrogen, alkyl of C ₁ -C _10, alkyl halide C ₁ ~C _10, C ₆ ~C ₂₀ aryls and C ₆ -C ₂₀ aryl halides are shown respectively. (These alkyls and aryls may have a substituent or a hetero atom in the structure, and a plurality of R ³ and R ⁴ are respectively present. May combine to form a ring. }, And a mixed solvent obtained by mixing N-methyl-N′-propylpiperidinium bis (trifluoromethanesulfonyl) imide, ethylene carbonate and diethyl carbonate in a volume ratio of 20:30:50, LiPF ₆ as an electrolyte Excluding non-aqueous electrolyte solution only dissolved. ) Nonaqueous electrolyte battery according to claim.   2. The nonaqueous electrolyte battery according to claim 1, wherein the “organic compound that is liquid at normal temperature” contains an ionic liquid in an amount of 30% by mass to less than 70% by mass.   3. The nonaqueous electrolyte battery according to claim 1, wherein the “organic compound that is liquid at normal temperature” contains cyclic carbonate and / or chain carbonate in an amount of more than 30 mass percent and 70 mass percent or less.   The “saturated aliphatic cyclic quaternary ammonium cation” constituting the ionic liquid includes N-methyl-N-ethylpiperidinium cation, N-methyl-N-propylpiperidinium cation, N-methyl-N-butylpi The nonaqueous electrolyte battery according to any one of claims 1 to 3, wherein the battery is at least one of cations selected from a peridinium cation and an N-methyl-N-hexylpiperidinium cation. The negative active material used for the negative electrode, a nonaqueous electrolyte battery according to any one of claims 1-4, characterized in that the carbonaceous material.