JPWO2014171518A1 - Lithium ion secondary battery - Google Patents

Abstract

A lithium ion secondary battery having a positive electrode and a negative electrode capable of occluding and releasing lithium, and a non-aqueous electrolyte containing lithium ions, wherein the non-aqueous electrolyte is propylene carbonate, fluorine represented by the general formula (1) Containing one or more selected from a fluorinated cyclic carbonate, and a fluorine-containing phosphate ester and a fluorinated chain ether, and the content of the propylene carbonate is 1% by volume to 50% by volume in the nonaqueous electrolyte solvent Further, the present invention relates to a lithium ion secondary battery, wherein the content of the fluorinated cyclic carbonate is 0.1% by volume or more and 10% by volume or less in the nonaqueous electrolytic solvent. ADVANTAGE OF THE INVENTION According to this invention, the secondary battery which was excellent in the low temperature characteristic and the gas generation was suppressed can be provided.

Description

  The present invention relates to a secondary battery, in particular, a lithium ion secondary battery, and more particularly to an electrolyte for a secondary battery, a lithium ion secondary battery using the same, and a method for manufacturing the same.

  Lithium secondary batteries are widely used in applications such as portable electronic devices and personal computers. Lithium secondary batteries are required to have improved safety such as flame retardancy, and secondary batteries using an electrolytic solution containing a phosphate ester compound or a cyclic carbonate have been proposed as described in the following documents. .

  Patent Document 1 discloses a secondary battery using an electrolytic solution composed of a phosphate ester compound, a cyclic carbonate containing a halogen, a chain carbonate, and a lithium salt. Patent Document 1 shows that the use of this electrolytic solution can improve safety, and the irreversible capacity can be reduced by a combination of a carbon negative electrode and an electrolytic solution.

  Further, Patent Document 2 discloses an electrolyte for an alkali metal ion secondary battery containing a solution of fluoroethylene carbonate, an alkali metal dissolved therein, and propylene carbonate. By using this electrolyte, a secondary battery is disclosed. It has been shown that irreversible capacity loss and battery efficiency reduction can be suppressed.

  Patent Document 3 shows that by mixing a phosphate ester, high safety can be ensured even when lithium metal is deposited on the negative electrode.

  Patent Document 4 discloses a secondary battery using an electrolytic solution containing a phosphate ester, a cyclic carbonate, and either a vinylene carbonate compound or a vinylethylene carbonate compound.

  In patent document 5, the secondary battery which has the electrolyte solution containing the phosphate ester containing a fluorine is disclosed.

Patent Document 6 and Patent Document 7 include the formula R ¹ O— (R ² O) _n —R ³ (R ¹ , R ³ : an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, R ² : an alkylene group having 1 to 8 carbon atoms which may be substituted with a halogen atom, provided that at least one of R ¹ , R ² and R ³ must be substituted with a halogen atom, 1 ≦ n ≦ A secondary battery using an electrolytic solution containing glycol diether represented by 4) is disclosed. Furthermore, Patent Document 6 and Patent Document 7 disclose that a phosphate ester is contained in an electrolytic solution, but there is no description regarding a fluorinated phosphate ester.

  Further, in the lithium secondary battery, safety is required, but improvement of the energy density of the battery is an important technical problem.

Several methods are conceivable as methods for increasing the energy density of the lithium secondary battery. Among them, it is effective to increase the operating potential of the battery. In a lithium secondary battery using conventional lithium cobaltate or lithium manganate as a positive electrode active material, the operating potential is 4V class (average operating potential = 3.6 to 3.8V: lithium potential). This is because the expression potential is defined by the redox reaction of Co ions or Mn ions (Co ³⁺ ← → Co ⁴⁺ or Mn ³⁺ ← → Mn ⁴⁺ ).

On the other hand, for example, it is known that an operating potential of 5 V class can be realized by using, as an active material, a spinel compound in which Mn of lithium manganate is substituted with Ni or the like. Specifically, as in Patent Document 8, it is known that a spinel compound such as LiNi _0.5 Mn _1.5 O ₄ exhibits a potential plateau in a region of 4.5 V or higher. In such a spinel compound, Mn exists in a tetravalent state, and the operating potential is defined by oxidation and reduction of Ni ²⁺ ← → Ni ⁴⁺ instead of oxidation reduction of Mn ³⁺ ← → Mn ⁴⁺ .

LiNi _0.5 Mn _1.5 O ₄ has a capacity of 130 mAh / g or more and an average operating voltage of 4.6 V or more with respect to metallic lithium. Although the capacity is smaller than LiCoO ₂ , the energy density of the battery is higher than LiCoO ₂ . For these reasons, LiNi _0.5 Mn _1.5 O ₄ is promising as a future positive electrode material.

Japanese Patent No. 39615197 JP-T-2001-501355 Japanese Patent No. 3812495 Japanese Patent No. 4187965 JP 2008-021560 A JP 2001-023691 A JP 2001-085056 A JP 2009-123707 A

J. et al. Electrochem. Soc. , Vol. 144, 204 (1997)

  Among the aforementioned cyclic carbonates, ethylene carbonate (EC) has a very large dielectric constant of 90, and is known to have a great effect of ionizing lithium salt to generate ions that carry electricity. However, since ethylene carbonate has a high melting point of 37 ° C. and is a solid at the operating temperature of the battery alone, it can cause lithium ions to become difficult to move at low temperatures, and can precipitate and affect the characteristics. Was expected. In contrast, propylene carbonate (PC) has a fairly large dielectric constant of 65 and a melting point of −49 ° C., so it does not precipitate even at low temperatures, and can maintain the ionization of lithium salts and the mobility of ions. There is.

  However, it is known that propylene carbonate reacts with carbon used as a general negative electrode material to degrade the negative electrode or generate gas.

On the other hand, as the positive electrode active material, there is a 4V class material such as LiMn ₂ O ₄ or LiCoO ₂ as disclosed in Patent Documents 1 to 7 described above. Further, as disclosed in Patent Document 8, when a spinel compound such as LiNi _0.5 Mn _1.5 O ₄ is used as a positive electrode active material, a higher operating voltage can be obtained. However, under a high operating voltage, the reaction between the PC and the negative electrode is more likely to proceed. Since gas is generated by this reaction, there are problems in practical use such as an increase in the internal pressure of the cell in a cycle operation and swelling of the laminate cell. In addition, there is a problem that capacity and cycle characteristics are reduced due to decomposition of the electrolytic solution and deterioration of the negative electrode.

  An object of this invention is to provide the lithium secondary battery which was excellent in the low temperature characteristic and the gas generation was suppressed.

One embodiment of the present invention provides:
A lithium ion secondary battery having a positive electrode and a negative electrode capable of occluding and releasing lithium, and a non-aqueous electrolyte containing lithium ions,
The non-aqueous electrolyte is propylene carbonate,
A fluorinated cyclic carbonate represented by the general formula (1), and
Containing one or more selected from fluorine-containing phosphate esters and fluorinated chain ethers,
The content of the propylene carbonate is 1% by volume to 50% by volume in the nonaqueous electrolytic solvent, and the content of the fluorinated cyclic carbonate is 0.1% by volume to 10% by volume in the nonaqueous electrolytic solvent. The present invention relates to a lithium ion secondary battery.

［式（１）中、ＡからＤは、それぞれ独立に、水素原子、フッ素原子、または、置換もしくは無置換のアルキル基であり、ＡからＤの少なくとも１つはフッ素原子またはフッ素含有アルキル基である。］

[In the formula (1), A to D are each independently a hydrogen atom, a fluorine atom, or a substituted or unsubstituted alkyl group, and at least one of A to D is a fluorine atom or a fluorine-containing alkyl group. is there. ]

  According to the present invention, it is possible to provide a lithium ion secondary battery that has excellent low-temperature characteristics and gas generation is suppressed.

It is a figure which shows the cross-section of the secondary battery which concerns on this embodiment. It is a graph which shows the gas generation amount after a charging / discharging cycle in the Example of this invention.

  The lithium secondary battery of this embodiment has a positive electrode, a negative electrode, and an electrolytic solution containing a nonaqueous electrolytic solvent. The nonaqueous electrolytic solvent is one or more selected from propylene carbonate (hereinafter also referred to as PC), a fluorinated cyclic carbonate represented by the above formula (1), and a fluorine-containing phosphate ester and a fluorinated chain ether. Is included. In the lithium secondary battery of this embodiment, a positive electrode active material that operates at a 4 V class (for example, an average operating potential of 3.6 to 3.8 V: with respect to lithium potential) may be used. A positive electrode active material that operates at a potential of 5 V or higher may be used. The negative electrode active material preferably contains carbon.

(Electrolyte)
The nonaqueous electrolyte (hereinafter also referred to as “electrolytic solution” or “nonaqueous electrolytic solution”) includes a supporting salt and a nonaqueous electrolytic solvent, and the nonaqueous electrolytic solvent is represented by propylene carbonate, the above formula (1). Fluorinated cyclic carbonate, and at least one selected from fluorine-containing phosphate esters and fluorinated chain ethers are included.

  In this embodiment, the nonaqueous electrolytic solvent includes propylene carbonate (PC). Although the content rate of PC contained in a nonaqueous electrolytic solvent is not restrict | limited in particular, It is preferable that they are 1 volume% or more and 50 volume% or less in a nonaqueous electrolytic solvent. When the content of PC in the nonaqueous electrolytic solvent is 1% by volume or more, the effect of increasing the ionization of the lithium salt is further improved, and it is more preferably 5% by volume or more. Since propylene carbonate (PC) may react with carbon to cause deterioration of the negative electrode or generate gas, it is generally difficult to use PC as a nonaqueous electrolytic solvent. However, since the reaction between PC and carbon is suppressed in the nonaqueous electrolytic solvent of the present invention, the reaction with the negative electrode containing carbon is reduced if the PC content in the nonaqueous electrolytic solvent is 50% by volume or less. can do. The content of PC is more preferably 40% by volume or less in the nonaqueous electrolytic solvent, and further preferably 30% by volume or less.

  In this embodiment, the nonaqueous electrolytic solvent contains a fluorinated cyclic carbonate represented by the following formula (1).

式（１）で表されるフッ素化環状カーボネートにおいて、Ａ、Ｂ、ＣおよびＤは、それぞれ独立に、水素原子、フッ素原子、または、置換もしくは無置換のアルキル基であって、Ａ、Ｂ、ＣおよびＤの少なくとも１つはフッ素原子またはフッ素含有アルキル基である。

In the fluorinated cyclic carbonate represented by the formula (1), A, B, C and D are each independently a hydrogen atom, a fluorine atom, or a substituted or unsubstituted alkyl group, and A, B, At least one of C and D is a fluorine atom or a fluorine-containing alkyl group.

  In Formula (1), the number of carbon atoms of the alkyl group represented by A, B, C, or D is preferably 1 or more and 4 or less, and more preferably 1 or more and 3 or less. When the carbon number of the alkyl group is 4 or less, the increase in the viscosity of the electrolytic solution is suppressed, and the electrolytic solution can easily penetrate into the pores in the electrode and the separator, and the ion conductivity is improved. This is because the current value becomes favorable in the discharge characteristics.

  The fluorine-containing alkyl group represents an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number and position of substitution of the fluorine atom are arbitrary. In the present embodiment, at least one of A to D is preferably a fluorine atom or a fluorine-containing alkyl group in which 50% or more of the hydrogen atoms of the corresponding unsubstituted alkyl group are substituted with fluorine atoms. . Further, all of A to D are fluorine atoms or fluorine-containing alkyl groups, and A to D are fluorine atoms or fluorine atoms in which 50% or more of the hydrogen atoms of the corresponding unsubstituted alkyl group are substituted with fluorine atoms. A containing alkyl group is also preferred. When the content of fluorine atoms is large, the voltage resistance is further improved, and even when a positive electrode active material that operates at a potential of 4.5 V or higher with respect to lithium is used, the deterioration of battery capacity after cycling is further reduced. Because it can.

  A to D may have a substituent in addition to the fluorine atom. Examples of the substituent include an amino group, a carboxy group, a hydroxy group, a cyano group, and a halogen atom (for example, a chlorine atom, a bromine atom). ) At least one selected from the group consisting of: In addition, said carbon number is the concept also including a substituent.

  Examples of the fluorinated cyclic carbonate include compounds in which some or all of the hydrogen atoms such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) are substituted with fluorine atoms. For example, 4-fluoro-1,3-dioxolan-2-one (FEC) in which one hydrogen of ethylene carbonate (EC) is substituted by fluorine, and two in which fluorine is substituted (cis or trans) 4,5- 4,4,5,5-tetrafluoro-1,3-difluoro-1,3-dioxolan-2-one, 4,4-difluoro-1,3-dioxolan-2-one, four substituted with fluorine Dioxolan-2-one and 4-fluoromethyl-1,3-dioxolan-2-one, 4-fluoro-5-methyl-1,3-, in which one of the hydrogen atoms of propylene carbonate (PC) is substituted with fluorine Dioxolan-2-one, 4-fluoro-4-methyl-1,3-dioxolan-2-one, 3,3,3-trifluoropropylene carbonate with three substituted fluorines (F C), and the like.

  The content of the fluorinated cyclic carbonate contained in the nonaqueous electrolytic solvent is not particularly limited, but is preferably 0.1% by volume or more and 10% by volume or less in the nonaqueous electrolytic solvent. The effect which suppresses reaction of PC and a negative electrode improves more that the content rate in the nonaqueous electrolytic solvent of a fluorinated cyclic carbonate is 0.1 volume% or more. Further, when the content of the fluorinated cyclic carbonate in the nonaqueous electrolytic solvent is 10% by volume or less, gas generation due to the decomposition reaction of the fluorinated cyclic carbonate itself can be reduced. The content of the fluorinated cyclic carbonate in the nonaqueous electrolytic solvent is more preferably 1% by volume or more, further preferably 1.5% by volume or more, and particularly preferably 2% by volume or more. The content of the fluorinated cyclic carbonate in the nonaqueous electrolytic solvent is more preferably 5% by volume or less.

  Moreover, it is preferable that the content rate of the fluorinated cyclic carbonate with respect to propylene carbonate (PC) is 2 volume% or more, and 4 volume% or more is more preferable. Moreover, it is preferable that the content rate of the fluorinated cyclic carbonate with respect to PC is 40 volume% or less, and 20 volume% or less is still more preferable.

  In the present embodiment, the non-aqueous electrolytic solvent is selected from the fluorine-containing phosphate ester represented by the following formula (2) and the fluorinated chain ether represented by the following formula (4) in addition to the fluorinated cyclic carbonate. May be included, and may include two or more. Hereinafter, each compound will be described.

  In the present embodiment, the nonaqueous electrolytic solvent can include a fluorine-containing phosphate ester represented by the following formula (2).

［式（２）において、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、アルキル基またはフッ素含有アルキル基を示し、Ｒ^１、Ｒ^２およびＲ^３の少なくとも１つがフッ素含有アルキル基である。］

[In Formula (2), R ¹ , R ² and R ³ each independently represents an alkyl group or a fluorine-containing alkyl group, and at least one of R ¹ , R ² and R ³ is a fluorine-containing alkyl group. ]

The fluorine-containing alkyl group is an alkyl group having at least one fluorine atom. In the formula ^(2), the number of carbon atoms in R 1, ^{R 2} and ^{R 3} each independently is preferably 1-3. At least one of R ¹ , R ² and R ³ is preferably a fluorine-containing alkyl group in which 50% or more of the hydrogen atoms of the corresponding unsubstituted alkyl group are substituted with fluorine atoms. Moreover, all of R ¹ , R ² and R ³ are fluorine-containing alkyl groups, and 50% or more of the hydrogen atoms of the unsubstituted alkyl group to which R ¹ , R ² and R ³ correspond are substituted with fluorine atoms. More preferably, it is a fluorine-containing alkyl group. When the content of fluorine atoms is large, the voltage resistance is further improved, and even when a positive electrode active material that operates at a potential of 4.5 V or higher with respect to lithium is used, the deterioration of battery capacity after cycling is further reduced. Because it can. The ratio of fluorine atoms in the substituent containing a hydrogen atom in the fluorine-containing alkyl group is more preferably 55% or more.

  Fluorine-containing phosphate ester is a solvent having low flammability and low reactivity. Although it does not specifically limit as a fluorine-containing phosphate ester, For example, phosphoric acid tris (trifluoromethyl), phosphoric acid tris (trifluoroethyl), phosphoric acid tris (tetrafluoropropyl), phosphoric acid tris (pentafluoropropyl) , Tris phosphate (heptafluorobutyl), tris phosphate (octafluoropentyl) and the like. Examples of the fluorine-containing phosphate ester include trifluoroethyldimethyl phosphate, bis (trifluoroethyl) methyl phosphate, bistrifluoroethylethyl phosphate, pentafluoropropyldimethyl phosphate, heptafluorobutyldimethyl phosphate, Trifluoroethylmethyl ethyl phosphate, pentafluoropropylmethyl ethyl phosphate, heptafluorobutylmethyl ethyl phosphate, trifluoroethyl methyl propyl phosphate, pentafluoropropyl methyl propyl phosphate, heptafluorobutyl methyl propyl phosphate, phosphoric acid Trifluoroethylmethylbutyl, pentafluoropropylmethylbutyl phosphate, heptafluorobutylmethylbutyl phosphate, trifluoroethyldiethyl phosphate, pentafluoropropyldiethyl phosphate , Heptafluorobutyldiethyl phosphate, trifluoroethylethylpropyl phosphate, pentafluoropropylethylpropyl phosphate, heptafluorobutylethylpropyl phosphate, trifluoroethylethylbutyl phosphate, pentafluoropropylethylbutyl phosphate, phosphoric acid Heptafluorobutylethylbutyl, trifluoroethyldipropyl phosphate, pentafluoropropyldipropyl phosphate, heptafluorobutyldipropyl phosphate, trifluoroethylpropylbutyl phosphate, pentafluoropropylpropylbutyl phosphate, heptafluorophosphate Examples thereof include butylpropylbutyl, trifluoroethyl dibutyl phosphate, pentafluoropropyl dibutyl phosphate, heptafluorobutyl dibutyl phosphate and the like. Examples of tris (tetrafluoropropyl) phosphate include tris (2,2,3,3-tetrafluoropropyl) phosphate. Examples of tris phosphate (pentafluoropropyl) include tris phosphate (2,2,3,3,3-pentafluoropropyl). Examples of tris (trifluoroethyl) phosphate include tris (2,2,2-trifluoroethyl) phosphate (hereinafter also abbreviated as TTFEP). Examples of tris phosphate (heptafluorobutyl) include tris phosphate (1H, 1H-heptafluorobutyl). Examples of tris phosphate (octafluoropentyl) include tris phosphate (1H, 1H, 5H-octafluoropentyl). Among these, tris (2,2,2-trifluoroethyl) phosphate (TTFEP) represented by the following formula (3) is preferable because the effect of suppressing decomposition of the electrolytic solution at a high potential is high. A fluorine-containing phosphate ester can be used individually by 1 type or in combination of 2 or more types.

  The content of the fluorine-containing phosphate ester contained in the nonaqueous electrolytic solvent is not particularly limited, but is generally 0% by volume or more and 95% by volume or less in the nonaqueous electrolytic solvent, and 10% by volume or more and 95%. Volume% or less is preferable, 15 volume% or more and 80 volume% or less are more preferable, and 20 volume% or more and 70 volume% or less are more preferable. When the content of the fluorine-containing phosphate ester in the nonaqueous electrolytic solvent is 10% by volume or more, the effect of increasing the voltage resistance is further improved. Moreover, the ion conductivity of electrolyte solution improves that the content rate in the nonaqueous electrolytic solvent of fluorine-containing phosphate ester is 95 volume% or less, and the charging / discharging rate of a battery becomes more favorable.

  In the present embodiment, the non-aqueous electrolytic solvent can contain a fluorinated chain ether.

  The fluorinated chain ether is preferably used when a positive electrode that has high oxidation resistance and operates at a high potential is used. As a result, it is possible to improve the capacity maintenance rate of the charge / discharge cycle and reduce gas generation.

  Although it does not restrict | limit especially as a fluorinated chain | strand ether, For example, the structure which substituted one part or all part hydrogen atom of 1, 2- ethoxyethane (DEE) or ethoxymethoxyethane (EME) with the fluorine atom And the like. Specific examples of the fluorinated chain ether include 2,2,3,3,3-pentafluoropropyl-1,1,2,2-tetrafluoroethyl ether, 1,1,2, 2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1H, 1H, 2′H, 3H-decafluorodipropyl ether, 1,1,1,2,3,3-hexafluoropropyl-2 , 2-difluoroethyl ether, isopropyl-1,1,2,2-tetrafluoroethyl ether, propyl-1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2 , 2,3,3-tetrafluoropropyl ether (TFETFPE), 1H, 1H, 5H-perfluoropentyl-1,1,2,2-tetrafluoroethyl ether 1H, 1H, 2′H-perfluorodipropyl ether, 1H-perfluorobutyl-1H-perfluoroethyl ether, methyl perfluoropentyl ether, methyl perfluorohexyl ether, methyl-1,1,3,3 , 3-pentafluoro-2- (trifluoromethyl) propyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether, ethyl nonafluorobutyl ether, ethyl- 1,1,2,3,3,3-hexafluoropropyl ether, 1H, 1H, 5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether, 1H, 1H, 2′H-perfluoro Dipropyl ether, heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 2,2,3,3,3-pentafluoropropyl-1,1,2,2-tetrafluoro Examples include ethyl ether, ethyl nonafluorobutyl ether, and methyl nonafluorobutyl ether. Among these, from the viewpoint of withstand voltage and boiling point, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1H, 1H, 2′H, 3H-decafluoro Dipropyl ether, 1H, 1H, 2′H-perfluorodipropyl ether, ethyl nonafluorobutyl ether and the like are preferable.

  The chain ether has the effect of reducing the viscosity of the electrolytic solution, like the chain carbonate. Therefore, for example, a chain ether can be used in place of a chain carbonate or carboxylic acid ester, and can also be used in combination with a chain carbonate or carboxylic acid ester.

  Since chain ether tends to have a low boiling point when the number of carbon atoms is small, the chain ether may vaporize during high-temperature operation of the battery. On the other hand, if the number of carbon atoms is too large, the viscosity of the chain ether increases, and the conductivity of the electrolytic solution may decrease. Accordingly, the number of carbon atoms is preferably 4 or more and 10 or less. For this reason, in the present embodiment, the fluorinated chain ether is preferably represented by the following formula (4).

_{C n H 2n + 1-l} F l -O-C m H 2m + 1-k F k (4)
[In the formula (4), n is 1, 2, 3, 4, 5 or 6, m is 1, 2, 3 or 4, l is any integer from 0 to 2n + 1, and k Is an integer from 0 to 2m + 1, and at least one of l and k is an integer of 1 or more. ]

  In the fluorinated chain ether represented by the formula (4), if the amount of fluorine substitution is small, the fluorinated chain ether reacts with the positive electrode having a high potential, so that the capacity retention rate of the battery is reduced or gas is generated. Sometimes. On the other hand, if the amount of fluorine substitution is too large, the compatibility of the fluorinated chain ether with other solvents may decrease, or the boiling point of the fluorinated chain ether may decrease. For these reasons, the fluorine substitution amount is preferably 10% or more and 90% or less, more preferably 20% or more and 85% or less, and further preferably 30% or more and 80% or more. That is, it is preferable that l, m, and n in Expression (4) satisfy the following relational expression.

  0.1 ≦ (l + k) / (2n + 2m + 2) ≦ 0.9

  The content of the fluorinated chain ether is not particularly limited, but is preferably 0.1% by volume or more and 70% by volume or less in the nonaqueous electrolytic solvent. When the content of the fluorinated chain ether in the nonaqueous electrolytic solvent is 0.1% by volume or more, the viscosity of the electrolytic solution can be lowered and the conductivity can be increased. Moreover, the effect which improves oxidation resistance is acquired. Further, when the content of the fluorinated chain ether in the nonaqueous electrolytic solvent is 70% by volume or less, it is possible to keep the conductivity of the electrolytic solution high and to ensure the compatibility of the electrolytic solution. Can do. The content of the fluorinated chain ether in the nonaqueous electrolytic solvent is more preferably 1% by volume or more, further preferably 5% by volume or more, and particularly preferably 10% by volume or more. The content of the fluorinated chain ether in the nonaqueous electrolytic solvent is more preferably 65% by volume or less, further preferably 60% by volume or less, and particularly preferably 55% by volume or less.

  Fluorinated chain ethers may be used singly or in combination of two or more.

  In the present embodiment, the nonaqueous electrolytic solvent may include the following in addition to the above.

  The nonaqueous electrolytic solvent may contain a fluorinated diether compound having low flammability and low reactivity.

Formula (5):
R ₁ O— (R ₂ O) _n —R ₃ (5)
In the fluorinated diether compound represented by the formula: R ₁ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom, and R ₂ is substituted with a fluorine atom. And an alkylene group having 1 to 4 carbon atoms, wherein at least one of hydrogen atoms contained in R ₁ , R ₂ and R ₃ is substituted with a fluorine atom.

The number of carbon atoms of R ₁ and R ₃ is more preferably 1 or more and 3 or less. In a preferred embodiment, R ₁ and R ₃ are fluorine-containing alkyl groups such as trifluoromethyl, trifluoroethyl, tetrafluoropropyl, pentafluoropropyl and heptafluorobutyl. The fluorine substitution position is arbitrary, and examples thereof include 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl and the like. Although it can, it is not limited to these.

The number of carbon atoms of R ₂ is more preferably 1 or more and 3 or less. Examples include methylene, ethylene, 1,2-propylene, 1,3-propylene, butylene and their fluorine substituents. In particular, ethylene, 1,2-propylene and 1,3-propylene are preferable. In a preferred embodiment, R ₂ is an unsubstituted alkylene group. n is preferably 1 or 2, and more preferably 1.

  The fluorinated diether compound is more preferably a compound represented by the following formula (6).

CF ₃ CH ₂ OCH ₂ CH ₂ OCH ₂ CF ₃ (6)

  When the fluorinated diether compound is contained, the content in the nonaqueous electrolytic solvent is not particularly limited, but is, for example, 0.1% by volume or more, more preferably 0.5% by volume or more, and further preferably It is 0.9 volume% or more. On the other hand, the upper limit of the content rate can be appropriately changed depending on the content of the fluorine-containing phosphate ester and the content of other organic solvents, and is typically 90% by volume or less, preferably 50% by volume or less. It is. The content of the fluorinated diether compound may be relatively small. Therefore, in a preferred embodiment, the content of the fluorinated diether compound is preferably 20% by volume, more preferably 10% by volume or less.

  The non-aqueous electrolyte can further include a cyclic carbonate or a chain carbonate.

  Since cyclic carbonate has a large relative dielectric constant, the dissociation property of the supporting salt is improved by addition, and sufficient conductivity is easily imparted. In addition, since the chain carbonate has a low viscosity, the viscosity of the electrolytic solution is lowered by addition, so that ion mobility in the electrolytic solution is improved. Cyclic carbonates and chain carbonates are suitable for mixing with fluorine-containing phosphate esters because of their high voltage resistance and electrical conductivity.

  The cyclic carbonate other than propylene carbonate is not particularly limited, and examples thereof include ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC).

  A cyclic carbonate can be used individually by 1 type or in combination of 2 or more types.

  When the cyclic carbonate is contained, the content in the nonaqueous electrolytic solvent is preferably 0.1% by volume or more, preferably 5% by volume from the viewpoints of increasing the dissociation degree of the supporting salt and increasing the conductivity of the electrolytic solution. The above is more preferable, 10% by volume or more is further preferable, and 15% by volume or more is particularly preferable. Further, from the same viewpoint, the content of the cyclic carbonate in the nonaqueous electrolytic solvent is preferably 70% by volume or less, more preferably 50% by volume or less, and further preferably 40% by volume or less.

  The chain carbonate is not particularly limited, and examples thereof include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and dipropyl carbonate (DPC). The chain carbonate includes a fluorinated chain carbonate. As the fluorinated chain carbonate, for example, a part or all of hydrogen atoms such as ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC) and the like are substituted with fluorine atoms. Examples include compounds having a structure. More specifically, examples of the fluorinated chain carbonate include bis (fluoroethyl) carbonate, 3-fluoropropyl methyl carbonate, 3,3,3-trifluoropropyl methyl carbonate, and 2,2,2-trifluoro. Ethyl methyl carbonate, 2,2,2-trifluoroethyl ethyl carbonate, monofluoromethyl methyl carbonate, methyl 2,2,3,3, tetrafluoropropyl carbonate, ethyl 2,2,3,3, tetrafluoropropyl carbonate, Bis (2,2,3,3, tetrafluoropropyl) carbonate, bis (2,2,2 trifluoroethyl) carbonate, 1-monofluoroethyl ethyl carbonate, 1-monofluoroethyl methyl carbonate, 2-monofluoroethyl Methyl car , Bis (1-mono-fluoroethyl) carbonate, bis (2-monofluoroethyl) carbonate, bis (monofluoromethyl) carbonate. Among these, dimethyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, monofluoromethyl methyl carbonate, methyl 2,2,3,3, tetrafluoropropyl carbonate and the like are preferable from the viewpoint of voltage resistance and conductivity. . A chain carbonate can be used individually by 1 type or in combination of 2 or more types.

  The chain carbonate has an advantage of low viscosity when the number of carbon atoms of the substituent added to the “—OCOO—” structure is small. On the other hand, if the number of carbon atoms is too large, the viscosity of the electrolytic solution may increase and the conductivity of Li ions may decrease. For these reasons, the total number of carbon atoms of the two substituents added to the “—OCOO—” structure of the chain carbonate is preferably 2 or more and 6 or less. Further, when the substituent added to the “—OCOO—” structure contains a fluorine atom, the oxidation resistance of the electrolytic solution is improved. For these reasons, the chain carbonate is preferably a fluorinated chain carbonate represented by the following formula (7).

_{C n H 2n + 1-l} F l -OCOO-C m H 2m + 1-k F k (7)
[In the formula (7), n is 1, 2 or 3, m is 1, 2 or 3, l is any integer from 0 to 2n + 1, and k is any from 0 to 2m + 1 And at least one of l and k is an integer of 1 or more. ]

  In the fluorinated chain carbonate represented by the formula (7), if the amount of fluorine substitution is small, the capacity retention rate of the battery is lowered or gas is generated due to the reaction of the fluorinated chain carbonate with the positive electrode of high potential. Sometimes. On the other hand, if the amount of fluorine substitution is too large, the compatibility of the chain carbonate with other solvents may decrease, or the boiling point of the chain carbonate may decrease. For these reasons, the fluorine substitution amount is preferably 1% or more and 90% or less, more preferably 5% or more and 85% or less, and further preferably 10% or more and 80% or less. That is, it is preferable that l, m, and n in Expression (7) satisfy the following relational expression.

  0.01 ≦ (l + k) / (2n + 2m + 2) ≦ 0.9

  The chain carbonate has an effect of lowering the viscosity of the electrolytic solution, and can increase the conductivity of the electrolytic solution. From these viewpoints, when the chain carbonate is contained, the content in the nonaqueous electrolytic solvent is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, and further preferably 1.0% by volume or more. preferable. Further, the content of the chain carbonate in the nonaqueous electrolytic solvent is preferably 90% by volume or less, more preferably 80% by volume or less, and further preferably 70% by volume or less.

  In addition, when the fluorinated chain carbonate is contained, the content in the nonaqueous electrolytic solvent is not particularly limited, but is preferably 0.1% by volume or more and 70% by volume or less. When the content of the fluorinated chain carbonate in the nonaqueous electrolytic solvent is 0.1% by volume or more, the viscosity of the electrolytic solution can be lowered and the conductivity can be increased. Moreover, the effect which improves oxidation resistance is acquired. Further, when the content of the fluorinated chain carbonate in the nonaqueous electrolytic solvent is 70% by volume or less, the conductivity of the electrolytic solution can be kept high. Further, the content of the fluorinated chain carbonate in the nonaqueous electrolytic solvent is more preferably 1% by volume or more, further preferably 5% by volume or more, and particularly preferably 10% by volume or more. The content of the fluorinated chain carbonate in the nonaqueous electrolytic solvent is more preferably 65% by volume or less, further preferably 60% by volume or less, and particularly preferably 55% by volume or less.

  Further, the nonaqueous electrolytic solvent may contain a carboxylic acid ester.

  The carboxylic acid ester is not particularly limited, and examples thereof include ethyl acetate, methyl propionate, ethyl formate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetate, and methyl formate. The carboxylic acid ester also includes a fluorinated carboxylic acid ester. Examples of the fluorinated carboxylic acid ester include ethyl acetate, methyl propionate, ethyl formate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetate, or formic acid. Examples thereof include compounds having a structure in which part or all of the hydrogen atoms of methyl are substituted with fluorine atoms. Specific examples of the fluorinated carboxylic acid ester include, for example, ethyl pentafluoropropionate, ethyl 3,3,3-trifluoropropionate, methyl 2,2,3,3-tetrafluoropropionate, and acetic acid. 2,2-difluoroethyl, methyl heptafluoroisobutyrate, methyl 2,3,3,3-tetrafluoropropionate, methyl pentafluoropropionate, 2- (trifluoromethyl) -3,3,3-trifluoropropion Methyl acetate, ethyl heptafluorobutyrate, methyl 3,3,3-trifluoropropionate, 2,2,2-trifluoroethyl acetate, isopropyl trifluoroacetate, tert-butyl trifluoroacetate, 4,4,4-tri Ethyl fluorobutyrate, methyl 4,4,4-trifluorobutyrate, 2,2-difluoro Acid butyl, ethyl difluoroacetate, n-butyl trifluoroacetate, 2,2,3,3-tetrafluoropropyl acetate, ethyl 3- (trifluoromethyl) butyrate, methyl tetrafluoro-2- (methoxy) propionate, 3 , 3,3-trifluoropropionic acid 3,3,3 trifluoropropyl, methyl difluoroacetate, 2,2,3,3-tetrafluoropropyl trifluoroacetate, 1H, 1H-heptafluorobutyl acetate, methyl heptafluorobutyrate And ethyl trifluoroacetate. Among these, from the viewpoints of withstand voltage and boiling point, as the carboxylic acid ester, ethyl propionate, methyl acetate, methyl 2,2,3,3-tetrafluoropropionate, 2,2,3,3 trifluoroacetic acid -Tetrafluoropropyl is preferred. Carboxylic acid esters have the effect of reducing the viscosity of the electrolytic solution in the same manner as chain carbonates. Therefore, for example, the carboxylic acid ester can be used in place of the chain carbonate, and can also be used in combination with the chain carbonate.

  The chain carboxylic acid ester has a feature that the viscosity is low when the number of carbon atoms of the substituent added to the “—COO—” structure is small, but the boiling point tends to be low. The chain carboxylic acid ester having a low boiling point may be vaporized when the battery is operated at a high temperature. On the other hand, if the number of carbon atoms is too large, the viscosity of the electrolytic solution may increase and conductivity may decrease. For these reasons, the total number of carbon atoms of the two substituents added to the “—COO—” structure of the chain carboxylic acid ester is preferably 3 or more and 8 or less.

  Further, when the substituent added to the “—COO—” structure contains a fluorine atom, the oxidation resistance of the electrolytic solution can be improved. For these reasons, the chain carboxylic acid ester is preferably a fluorinated chain carboxylic acid ester represented by the following formula (8).

_{C n H 2n + 1-l} F l -COO-C m H 2m + 1-k F k (8)
[In the formula (8), n is 1, 2, 3 or 4, m is 1, 2, 3 or 4, l is any integer from 0 to 2n + 1, and k is 0 to 2m + 1. And at least one of l and k is an integer of 1 or more. ]

  In the fluorinated chain carboxylic acid ester represented by the formula (8), when the amount of fluorine substitution is small, the capacity retention rate of the battery is lowered due to the reaction of the fluorinated chain carboxylic acid ester with the positive electrode of high potential, Gas may be generated. On the other hand, if the amount of fluorine substitution is too large, the compatibility of the chain carboxylic acid ester with other solvents may decrease, or the boiling point of the fluorinated chain carboxylic acid ester may decrease. For these reasons, the fluorine substitution amount is preferably 1% or more and 90% or less, more preferably 10% or more and 85% or less, and further preferably 20% or more and 80% or less. That is, it is preferable that l, m, and n in Expression (8) satisfy the following relational expression.

  0.01 ≦ (l + k) / (2n + 2m + 2) ≦ 0.9

  When the carboxylic acid ester is contained, the content in the nonaqueous electrolytic solvent is preferably 0.1 volume or more, more preferably 0.2 volume% or more, further preferably 0.5 volume% or more, and 1 volume% or more. Is particularly preferred. The content of the carboxylic acid ester in the nonaqueous electrolytic solvent is preferably 50% by volume or less, more preferably 20% by volume or less, still more preferably 15% by volume or less, and particularly preferably 10% by volume or less. By setting the content of the carboxylic acid ester to 0.1% by volume or more, the low temperature characteristics can be further improved, and the electrical conductivity can be further improved. Further, by setting the content of the carboxylic acid ester to 50% by volume or less, it is possible to reduce the vapor pressure from becoming too high when the battery is left at a high temperature.

  Moreover, when it contains fluorinated chain | strand-shaped carboxylic acid ester, the content rate in a non-aqueous electrolytic solvent is although it does not restrict | limit in particular, 0.1 volume% or more and 50 volume% or less are preferable. When the content of the fluorinated chain carboxylic acid ester in the nonaqueous electrolytic solvent is 0.1% by volume or more, the viscosity of the electrolytic solution can be lowered and the conductivity can be increased. Moreover, the effect which improves oxidation resistance is acquired. In addition, when the content of the fluorinated chain carboxylic acid ester in the nonaqueous electrolytic solvent is 50% by volume or less, the conductivity of the electrolytic solution can be kept high, and the compatibility of the electrolytic solution is ensured. Can do. The content of the fluorinated chain carboxylic acid ester in the nonaqueous electrolytic solvent is more preferably 1% by volume or more, further preferably 5% by volume or more, and particularly preferably 10% by volume or more. The content of the fluorinated chain carboxylic acid ester in the nonaqueous electrolytic solvent is more preferably 45% by volume or less, further preferably 40% by volume or less, and particularly preferably 35% by volume or less.

  The nonaqueous electrolytic solvent may contain an alkylene biscarbonate represented by the following formula (9). Since the oxidation resistance of the alkylene biscarbonate is equal to or slightly higher than that of the chain carbonate, the voltage resistance of the electrolytic solution can be improved.

［式（９）中、Ｒ_４およびＲ_６は、それぞれ独立に、置換または無置換のアルキル基を表す。Ｒ_５は、置換または無置換のアルキレン基を表す。］

[In Formula (9), R ₄ and R ₆ each independently represents a substituted or unsubstituted alkyl group. R ₅ represents a substituted or unsubstituted alkylene group. ]

  In the formula (9), the alkyl group includes a linear or branched group, preferably having 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkylene group is a divalent saturated hydrocarbon group, including a linear or branched group, preferably having 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. .

  Examples of the alkylene biscarbonate represented by the formula (9) include 1,2-bis (methoxycarbonyloxy) ethane, 1,2-bis (ethoxycarbonyloxy) ethane, and 1,2-bis (methoxycarbonyloxy). Examples include propane and 1-ethoxycarbonyloxy-2-methoxycarbonyloxyethane. Of these, 1,2-bis (methoxycarbonyloxy) ethane is preferred.

  When the alkylene biscarbonate is contained, the content in the nonaqueous electrolytic solvent is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, still more preferably 1% by volume or more, and 1.5% by volume. The above is particularly preferable. The content of the alkylene biscarbonate in the nonaqueous electrolytic solvent is preferably 70% by volume or less, more preferably 60% by volume or less, further preferably 50% by volume or less, and particularly preferably 40% by volume or less.

  Alkylene biscarbonate is a material having a low dielectric constant. Therefore, for example, it can be used in place of the chain carbonate, or can be used in combination with the chain carbonate.

  The non-aqueous electrolytic solvent can contain a chain ether.

  The chain ether is not particularly limited, and examples thereof include 1,2-ethoxyethane (DEE) and ethoxymethoxyethane (EME). The chain ether has the effect of reducing the viscosity of the electrolytic solution, like the chain carbonate. Therefore, for example, a chain ether can be used in place of a chain carbonate or carboxylic acid ester, and can also be used in combination with a chain carbonate or carboxylic acid ester.

  Since chain ether tends to have a low boiling point when the number of carbon atoms is small, the chain ether may vaporize during high-temperature operation of the battery. On the other hand, if the number of carbon atoms is too large, the viscosity of the chain ether increases, and the conductivity of the electrolytic solution may decrease. Accordingly, the number of carbon atoms is preferably 4 or more and 10 or less.

  In addition to the above, the nonaqueous electrolytic solvent may further include the following. The nonaqueous electrolytic solvent can include, for example, γ-lactones such as γ-butyrolactone, cyclic ethers such as tetrahydrofuran or 2-methyltetrahydrofuran, and the like. Moreover, what substituted some hydrogen atoms of these materials by the fluorine atom may be included. In addition, dimethyl sulfoxide, formamide, acetamide, dimethylformamide, dioxolane (for example, 1,3-dioxolane), acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, Aprotic organic solvents such as 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethyl ether, 1,3-propane sultone, anisole, N-methylpyrrolidone May be included.

Examples of the supporting salt include LiPF ₆ , LiAsF ₆ , LiAlCl ₄ , LiClO ₄ , LiBF ₄ , LiSbF ₆ , LiCF ₃ SO ₃ , LiC ₄ F ₉ CO ₃ , LiC (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ Examples thereof include lithium salts such as SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiB ₁₀ Cl ₁₀ . Other examples of the supporting salt include lower aliphatic lithium carboxylate carboxylate, lithium chloroborane, lithium tetraphenylborate, LiBr, LiI, LiSCN, LiCl, and the like. The supporting salt can be used alone or in combination of two or more.

  Further, an ion conductive polymer can be added to the nonaqueous electrolytic solvent. Examples of the ion conductive polymer include polyethers such as polyethylene oxide and polypropylene oxide, and polyolefins such as polyethylene and polypropylene. Examples of the ion conductive polymer include polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polymethyl acrylate, polyvinyl alcohol, polymethacrylonitrile, and polyvinyl chloride. Mention may be made of acetate, polyvinylpyrrolidone, polycarbonate, polyethylene terephthalate, polyhexamethylene acipamide, polycaprolactam, polyurethane, polyethyleneimine, polybutadiene, polystyrene, polyisoprene, and derivatives thereof. An ion conductive polymer can be used individually by 1 type or in combination of 2 or more types. Moreover, you may use the polymer containing the various monomers which comprise the said polymer.

  Moreover, in this embodiment, you may add electrolyte solution additive to a nonaqueous electrolytic solvent as needed.

(Positive electrode)
As the positive electrode active material, the positive electrode of the lithium secondary battery according to the present embodiment can use a 4V class material such as LiMn ₂ O ₄ or LiCoO ₂ as disclosed in Patent Documents 1 to 6 described above. . LiM1O ₂ (M1 is at least one element selected from the group consisting of Mn, Fe, Co, and Ni, and a part of M1 may be substituted with Mg, Al, or Ti), LiMn Lithium such as _2-x M2 _x O ₄ (M2 is at least one element selected from the group consisting of Mg, Al, Co, Ni, Fe, and B, and 0 ≦ x <0.4). Containing complex oxides, olivine type materials represented by LiFePO ₄ and the like can also be used.

  Further, from the viewpoint of obtaining a high energy density, it is preferable to include a positive electrode active material that can occlude or release lithium ions at a potential of 4.5 V or more with respect to lithium metal. As such a positive electrode active material, a material in which at least a charge curve of the charge / discharge curve has a region of 4.5 V or more with respect to lithium metal at least in part can be used. That is, an active material having at least a region of 4.5 V or more with respect to lithium metal only in the charge curve, or at least a region of 4.5 V or more with respect to lithium metal in both the charge curve and the discharge curve Can be used.

  As measurement conditions for this charge / discharge curve, the charge / discharge current can be set to 5 mA / g per mass of the positive electrode active material, the charge end voltage can be set to 5.2V, and the discharge end voltage can be set to 3V.

  Examples of such positive electrode active materials include spinel materials, layered materials, and olivine materials.

As a spinel-based material, LiNi _0.5 Mn _1.5 O ₄ , LiCoMnO ₄ , LiCrMnO ₄ , LiFeMnO ₄ , LiCu _0.5 Mn _1.5 O _{4 and the} like with a high potential of 4.5 V or higher. materials operates; a part of Mn of LiMn ₂ O ₄ with increased substitution to life with another _{element, LiM1 x Mn 2-x-} y M2 y O 4 (M1 is Ni, Fe, Co, Cr, and Cu At least one selected, 0.4 <x <1.1, M2 is at least one selected from Li, Al, B, Mg, Si and transition metals, and 0 <y <0. 5)); and those obtained by substituting a part of oxygen of these materials with fluorine or chlorine.

  As the spinel material, a material represented by the following formula (10) is particularly preferable.

Li _a (M _x Mn _2−xy Y _y ) (O _4−w Z _w ) (10)
[In formula (10), 0 ≦ x ≦ 1.2, 0 ≦ y, x + y <2, 0 ≦ a ≦ 1.2, 0 ≦ w ≦ 1, and M is Co, Ni, Fe, Cr and Cu. Y is at least one selected from Li, B, Na, Al, Mg, Ti, Si, K and Ca, and Z is at least one of F and Cl. ]

  It is particularly preferable that 0.4 ≦ x ≦ 1.1.

The layered material is represented by a general formula LiMO ₂ , specifically, LiCoO ₂ , LiNi _1-x M _x O ₂ (0.05 <x <0.3, where M is an element containing at least Co or Al. there. material represented _{by), Li (Ni x Co y} Mn 2-x-y) O 2 (0.1 <x <0.7,0 <y <0.5), Li (M 1-z And a material represented by Mn _z ) O ₂ (0.33 ≦ z ≦ 0.7, M is at least one of Li, Co, and Ni).

  Moreover, the material represented by the following formula (11) is particularly preferable.

_{Li (Li x M 1-x} -z Mn z) O 2 (11)
[In formula (11), 0 ≦ x <0.3, 0.3 ≦ z ≦ 0.7, and M is at least one of Co and Ni. ]

X in the formula (11) is preferably 0 ≦ x <0.2.

The olivine-based material has the general formula:
LiMPO ₄ (M is a transition metal)
Specifically, LiFePO ₄ , LiMnPO ₄ , LiCoPO ₄ , and LiNiPO ₄ may be mentioned. Those in which a part of these transition metals is replaced with another element or the oxygen part is replaced with fluorine can also be used. From the viewpoint of high energy density, a material represented by LiMPO ₄ (M is at least one of Co and Ni) operating at a high potential is preferable.

  In addition, NASICON type, lithium transition metal silicon composite oxide, and the like can be used.

  The positive electrode active material that operates at the above high potential may be used in combination with other normal positive electrode active materials, but the content of the positive electrode active material that operates at the above high potential in the entire positive electrode active material is 60% by mass. The above is preferable, 80% by mass or more is more preferable, and 90% by mass or more is further preferable.

Specific surface areas of these positive electrode active materials are, for example, 0.01 to ⁵ m ² / g, preferably 0.05 to ⁴ m ² / g, more preferably 0.1 to ³ m ² / g, and 0.2 to ² m. ² / g is more preferable. By setting the specific surface area in such a range, the contact area with the electrolytic solution can be adjusted to an appropriate range. That is, by setting the specific surface area to 0.01 m ² / g or more, lithium ions can be easily inserted and desorbed smoothly, and the resistance can be further reduced. Moreover, by making a specific surface area 5 m < ² > / g or less, decomposition | disassembly of electrolyte solution can be accelerated | stimulated and it can suppress more that the constituent element of an active material elutes. The specific surface area can be measured by a usual BET specific surface area measurement method.

The center particle diameter of the positive electrode active material is preferably 0.01 to 50 μm, and more preferably 0.02 to 40 μm. By setting the particle size to 0.02 μm or more, elution of constituent elements of the positive electrode active material can be further suppressed, and deterioration due to contact with the electrolytic solution can be further suppressed. In addition, when the particle size is 50 μm or less, lithium ions can be easily inserted and desorbed smoothly, and the resistance can be further reduced. The central particle diameter is 50% cumulative diameter D ₅₀ (median diameter), and can be measured by a laser diffraction / scattering particle size distribution analyzer.

  As the positive electrode binder, the same negative electrode binder can be used. Among these, polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost. The amount of the binder for positive electrode to be used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoints of binding force and energy density in a trade-off relationship.

  As binders other than polyvinylidene fluoride (PVdF), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polytetrafluoroethylene, polypropylene, Examples include polyethylene, polyimide, and polyamideimide.

  A conductive auxiliary material may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of reducing impedance. Examples of the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.

  As the positive electrode current collector, aluminum, nickel, silver, and alloys thereof are preferable. Examples of the shape include foil, flat plate, and mesh.

  The positive electrode is obtained by dispersing and kneading the above active material together with a conductive material and a binder in a solvent such as N-methyl-2-pyrrolidone (NMP), and applying this onto a positive electrode current collector. Can do.

(Negative electrode)
A negative electrode will not be specifically limited if the negative electrode active material contains the material which can occlude and discharge | release lithium.

  The negative electrode active material is not particularly limited. For example, a carbon material (a) that can occlude and release lithium ions, a metal (b) that can be alloyed with lithium, or a metal that can occlude and release lithium ions. An oxide (c) etc. are mentioned, It is preferable that a carbon material (a) is included.

  As the carbon material (a), graphite, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite thereof can be used. Here, graphite with high crystallinity has high electrical conductivity, and is excellent in adhesiveness and voltage flatness with a negative electrode current collector made of a metal such as copper. On the other hand, since amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs. The carbon material (a) can be used alone or in combination with other substances. When used in combination, the carbon material (a) is preferably in the range of 2% by mass to 80% by mass in the negative electrode active material, for example, in the range of 2% by mass to 30% by mass.

  As the metal (b), a metal mainly composed of Al, Si, Pb, Sn, Zn, Cd, Sb, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, La, or the like, or these Two or more kinds of alloys, or an alloy of these metals or alloys and lithium can be used. In particular, silicon (Si) is preferably included as the metal (b). The metal (b) can be used alone or in combination with other substances, but is preferably in the range of 5% by mass to 90% by mass in the negative electrode active material, and is 20% by mass to 50% by mass. The following range is more preferable.

  As the metal oxide (c), silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, or a composite thereof can be used. In particular, silicon oxide is preferably included as the metal oxide (c). This is because silicon oxide is relatively stable and hardly causes a reaction with other compounds. Moreover, 0.1-5 mass% of 1 type, or 2 or more types of elements chosen from nitrogen, boron, and sulfur can also be added to a metal oxide (c). By carrying out like this, the electrical conductivity of a metal oxide (c) can be improved. The metal oxide (c) can be used alone or in combination with other substances, but is preferably in the range of 5% by mass to 90% by mass in the negative electrode active material, and 40% by mass to 70% by mass. More preferably, it is in the range of mass% or less.

Specific examples of the metal oxide (c) include, for example, LiFe ₂ O ₃ , WO ₂ , MoO ₂ , SiO, SiO ₂ , CuO, SnO, SnO ₂ , Nb ₃ O ₅ , Li _x Ti _2−x O _4. (1 ≦ x ≦ 4/3), PbO ₂ , Pb ₂ O _{5 and the} like.

Other examples of the negative electrode active material include metal sulfide (d) that can occlude and release lithium ions. Metal sulfide as (d) are, for example, SnS and FeS ₂ or the like. In addition, as the negative electrode active material, for example, metallic lithium or lithium alloy, polyacene or polythiophene, or Li ₅ (Li ₃ N), Li ₇ MnN ₄ , Li ₃ FeN ₂ , Li _2.5 Co _0. Examples thereof include lithium nitride such as ₅ N or Li ₃ CoN.

  The above negative electrode active materials can be used singly or in combination of two or more.

  In one embodiment, the negative electrode active material may include a carbon material (a), a metal (b), and a metal oxide (c). Hereinafter, this negative electrode active material will be described.

  All or part of the metal oxide (c) preferably has an amorphous structure. The amorphous metal oxide (c) can suppress the volume expansion of the carbon material (a) and the metal (b), and can suppress the decomposition of the electrolytic solution. This mechanism is presumed to have some influence on the film formation on the interface between the carbon material (a) and the electrolytic solution due to the amorphous structure of the metal oxide (c). The amorphous structure is considered to have relatively few elements due to non-uniformity such as crystal grain boundaries and defects. In addition, it can be confirmed by X-ray diffraction measurement (general XRD measurement) that all or part of the metal oxide (c) has an amorphous structure. Specifically, when the metal oxide (c) does not have an amorphous structure, a peak specific to the metal oxide (c) is observed, but all or part of the metal oxide (c) is amorphous. In the case of having a structure, the intrinsic peak of the metal oxide (c) is broad and observed.

  The metal oxide (c) is preferably a metal oxide constituting the metal (b). The metal (b) and the metal oxide (c) are preferably silicon (Si) and silicon oxide (SiO), respectively.

  It is preferable that all or part of the metal (b) is dispersed in the metal oxide (c). By dispersing at least a part of the metal (b) in the metal oxide (c), the volume expansion of the whole negative electrode can be further suppressed, and the decomposition of the electrolytic solution can also be suppressed. Note that all or part of the metal (b) is dispersed in the metal oxide (c) because it is observed with a transmission electron microscope (general TEM observation) and energy dispersive X-ray spectroscopy (general). This can be confirmed by using a combination of a standard EDX measurement. Specifically, the cross section of the sample containing the metal (b) particles is observed, the oxygen concentration of the metal (b) particles dispersed in the metal oxide (c) is measured, and the metal (b) particles are configured. It can be confirmed that the metal being used is not an oxide.

  As described above, the content of each carbon material (a), metal (b), and metal oxide (c) with respect to the total of the carbon material (a), metal (b), and metal oxide (c) is These are preferably 2 to 80% by mass, 5 to 90% by mass, and 5 to 90% by mass, respectively. Moreover, the content rate of each carbon material (a), a metal (b), and a metal oxide (c) with respect to the sum total of a carbon material (a), a metal (b), and a metal oxide (c), respectively, More preferably, they are 2 mass% or more and 30 mass% or less, 20 mass% or more and 50 mass% or less, and 40 mass% or more and 70 mass% or less.

  A negative electrode active material in which all or part of the metal oxide (c) has an amorphous structure and all or part of the metal (b) is dispersed in the metal oxide (c) is disclosed in, for example, It can be produced by a method as disclosed in 2004-47404. That is, by performing a CVD process on the metal oxide (c) in an atmosphere containing an organic gas such as methane gas, the metal (b) in the metal oxide (c) is nanoclustered and the surface is a carbon material (a ) Can be obtained. Moreover, the said negative electrode active material is producible also by mixing a carbon material (a), a metal (b), and a metal oxide (c) by mechanical milling.

  The carbon material (a), the metal (b), and the metal oxide (c) are not particularly limited, but particulate materials can be used. For example, the average particle diameter of the metal (b) may be smaller than the average particle diameter of the carbon material (a) and the average particle diameter of the metal oxide (c). In this way, the metal (b) having a large volume change during charging and discharging has a relatively small particle size, and the carbon material (a) and the metal oxide (c) having a small volume change have a relatively large particle size. Therefore, dendrite formation and alloy pulverization are more effectively suppressed. In addition, lithium is occluded and released in the order of large-diameter particles, small-diameter particles, and large-diameter particles during the charge / discharge process. This also suppresses the occurrence of residual stress and residual strain. Is done. The average particle diameter of the metal (b) can be, for example, 20 μm or less, and is preferably 15 μm or less.

  Moreover, it is preferable that the average particle diameter of a metal oxide (c) is 1/2 or less of the average particle diameter of a carbon material (a), and the average particle diameter of a metal (b) is an average of a metal oxide (c). It is preferable that it is 1/2 or less of a particle diameter. Furthermore, the average particle diameter of the metal oxide (c) is ½ or less of the average particle diameter of the carbon material (a), and the average particle diameter of the metal (b) is the average particle diameter of the metal oxide (c). It is more preferable that it is 1/2 or less. By controlling the average particle size in such a range, the effect of relaxing the volume expansion of the metal and alloy phases can be obtained more effectively, and a secondary battery having an excellent balance of energy density, cycle life and efficiency can be obtained. Can do. More specifically, the average particle diameter of the silicon oxide (c) is set to 1/2 or less of the average particle diameter of the graphite (a), and the average particle diameter of the silicon (b) is the average particle of the silicon oxide (c). It is preferable to make it 1/2 or less of the diameter. More specifically, the average particle diameter of silicon (b) can be, for example, 20 μm or less, and is preferably 15 μm or less.

  The binder for the negative electrode is not particularly limited, but polyvinylidene fluoride (PVdF), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer. Polymerized rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamideimide and the like can be mentioned.

  The content of the negative electrode binder is preferably in the range of 1 to 30% by mass and more preferably 2 to 25% by mass with respect to the total amount of the negative electrode active material and the negative electrode binder. By setting the content to 1% by mass or more, the adhesion between the active materials or between the active material and the current collector is improved, and the cycle characteristics are improved. Moreover, by setting it as 30 mass% or less, an active material ratio can improve and a negative electrode capacity | capacitance can be improved.

  Although it does not restrict | limit especially as a negative electrode electrical power collector, Aluminum, nickel, copper, silver, and those alloys are preferable from electrochemical stability. Examples of the shape include foil, flat plate, and mesh.

  The negative electrode can be produced by forming a negative electrode active material layer containing a negative electrode active material and a negative electrode binder on a negative electrode current collector. Examples of the method for forming the negative electrode active material layer include a doctor blade method, a die coater method, a CVD method, and a sputtering method. After forming a negative electrode active material layer in advance, a thin film of aluminum, nickel, or an alloy thereof may be formed by a method such as vapor deposition or sputtering to form a negative electrode current collector.

(Separator)
The secondary battery may be composed of a combination of a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte as its configuration. Examples of the separator include a woven fabric, a nonwoven fabric, a polyolefin polymer such as polyethylene and polypropylene, a polyimide, a porous polymer film such as a porous polyvinylidene fluoride film, or an ion conductive polymer electrolyte film. These can be used alone or in combination.

(Battery shape and exterior)
Examples of the shape of the battery include a cylindrical shape, a square shape, a coin shape, a button shape, and a laminate shape.

  In the case of the laminate type, the electrodes and the separator are laminated in a planar shape, and there is no portion with a small R (a region close to the winding core of the wound structure or a region corresponding to a folded portion of the flat wound structure). Therefore, when an active material having a large volume change associated with charging / discharging is used, it is less likely to be adversely affected by the volume change of the electrode associated with charging / discharging than a battery having a wound structure.

  Examples of the battery outer package include stainless steel, iron, aluminum, titanium, alloys thereof, and plated products thereof. As the plating, for example, nickel plating can be used. When the battery is a laminate type, a laminate film is preferable as the outer package.

  Examples of the metal foil layer on the resin base layer of the laminate film include aluminum, an aluminum alloy, and a titanium foil. Examples of the material for the heat-welded layer of the laminate film include thermoplastic polymer materials such as polyethylene, polypropylene, and polyethylene terephthalate. Moreover, the resin base material layer and the metal foil layer of the laminate film are not limited to one layer, but may be two or more layers. From the viewpoint of versatility and cost, an aluminum laminate film is preferable.

  When a laminate film is used as the outer package, battery volume changes and electrode distortions due to the generation of gas are more likely to occur than when a metal can is used as the outer package. This is because the laminate film is more easily deformed by the internal pressure of the battery than the metal can. In addition, when sealing a secondary battery using a laminate film as an exterior body, the internal pressure of the battery is usually lower than atmospheric pressure, and there is no extra space inside, so when gas is generated in the battery Immediately leads to battery volume change and electrode deformation. In addition, in the case of a laminate type battery, compared to a battery having a wound structure, when gas is generated between the electrodes, the gap between the electrodes tends to be widened because the gas tends to stay between the electrodes. When used, this tendency becomes more prominent. According to this embodiment, the occurrence of such a problem can be suppressed, and a non-aqueous electrolyte secondary battery excellent in long-term reliability is provided even for a laminated battery using a laminate film outer package. be able to.

(Basic battery structure)
A cross-sectional view of a laminated lithium secondary battery according to this embodiment is shown in FIG. As shown in FIG. 1, the lithium secondary battery according to the present embodiment includes a positive electrode current collector 3 made of a metal such as an aluminum foil and a positive electrode active material layer 1 containing a positive electrode active material provided thereon. And a negative electrode current collector 4 made of a metal such as copper foil and a negative electrode active material layer 2 containing a negative electrode active material provided thereon. The positive electrode and the negative electrode are laminated via a separator 5 made of a nonwoven fabric or a polypropylene microporous film so that the positive electrode active material layer 1 and the negative electrode active material layer 2 face each other. This electrode pair is accommodated in a container formed of exterior bodies 6 and 7 such as an aluminum laminate film. A positive electrode tab 9 is connected to the positive electrode current collector 3, and a negative electrode tab 8 is connected to the negative electrode current collector 4, and these tabs are drawn out of the container. An electrolytic solution is injected into the container and sealed. It can also be set as the structure where the electrode group by which the several electrode pair was laminated | stacked was accommodated in the container.

  EXAMPLES Hereinafter, specific examples to which the present invention is applied will be described. However, the present invention is not limited to the examples, and can be appropriately modified and implemented without departing from the gist thereof. .

  The abbreviations of the compounds used in the following examples are described.

PC: propylene carbonate EC: ethylene carbonate TFET FPE: 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether TTFEP: tris phosphate (2,2,2-trifluoroethyl)
DMC: dimethyl carbonate FEC: fluoroethylene carbonate FPC: 3,3,3-trifluoropropylene carbonate

<Example 1-1>
LiNi _0.5 Mn _1.5 O ₄ (90% by mass) as a positive electrode active material, polyvinylidene fluoride (PVdF) (5% by mass) as a binder, and carbon black (5% by mass) as a conductive agent ) And were mixed into a positive electrode mixture. This positive electrode mixture was dispersed in N-methyl-2-pyrrolidone to prepare a positive electrode slurry. This positive electrode slurry was uniformly applied to one side of an aluminum current collector having a thickness of 20 μm. The thickness of the coating film was adjusted so that the initial charge capacity per unit area was 2.5 mAh / cm ² . After drying, a positive electrode was produced by compression molding with a roll press.

Artificial graphite was used as the negative electrode active material. Artificial graphite was dispersed in PVDF dissolved in N-methylpyrrolidone to prepare a negative electrode slurry. The mass ratio of the negative electrode active material and the binder was 90/10. This negative electrode slurry was uniformly coated on a 10 μm thick Cu current collector. The thickness of the coating film was adjusted so that the initial charge capacity was 3.0 mAh / cm ² . After drying, a negative electrode was produced by compression molding with a roll press.

  A positive electrode and a negative electrode cut out to 3 cm × 3 cm were arranged so as to face each other with a separator interposed therebetween. As the separator, a microporous polypropylene film having a thickness of 25 μm was used.

The electrolytes are propylene carbonate (PC), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TFETFPE), tris phosphate (2,2,2-trifluoro). ethyl) (TTFEP), and dimethyl carbonate (DMC) in a solvent constituted by PC / TFETFPE / TTFEP / DMC = 50/30/20/3 ( volume ratio), the lithium salt LiPF ₆ 0.8 mol / l was added, Furthermore, fluoroethylene carbonate (FEC) was added so that the volume ratio was 2 in the solvent composition.

  The positive electrode, the negative electrode, the separator, and the electrolytic solution were placed in a laminate outer package, the laminate was sealed, and a lithium secondary battery was produced. The positive electrode and the negative electrode were connected to a tab and electrically connected from the outside of the laminate.

  This lithium secondary battery was charged at 100 mA, and after the upper limit voltage reached 4.8 V, it was charged at a constant voltage until the total charging time reached 2.5 hours. Thereafter, discharging was performed at a constant current until the lower limit voltage was 3 V at 100 mA. This charging / discharging was repeated 100 times. This charging / discharging was implemented in a 45 degreeC thermostat.

(Gas generation evaluation)
The amount of gas generation was evaluated by measuring the change in cell volume before and after the charge / discharge cycle. The cell volume was measured using the Archimedes method, and the gas generation amount was calculated by examining the difference before and after the charge / discharge cycle. Although not shown here, the amount of gas generated was very large when FEC was not added.

<Example 1-2>
A lithium secondary battery was produced in the same manner as in Example 1-1 except that fluoroethylene carbonate (FEC) was added so as to have a volume ratio of 3 in the solvent composition, and the amount of gas generated was measured.

<Example 1-3>
A lithium secondary battery was produced in the same manner as in Example 1-1 except that fluoroethylene carbonate (FEC) was added so as to have a volume ratio of 5 in the solvent composition, and the amount of gas generated was measured.

<Example 1-4>
A lithium secondary battery was produced in the same manner as in Example 1-1 except that fluoroethylene carbonate (FEC) was added so as to have a volume ratio of 10 in the solvent composition, and the amount of gas generated was measured.

  FIG. 2 shows the amount of gas generated in the charge / discharge cycle depending on the amount of fluoroethylene carbonate (FEC) that is a fluorinated cyclic carbonate (Examples 1-1 to 1-4). The gas generation amount is minimized by adding an appropriate amount of FEC, and tends to increase when it is further added. In this example, even in an electrolytic solvent composition containing PC in an amount of about 50% by volume, gas generation is well suppressed in the range where the content of FEC in the electrolytic solution is about 2 to 6% by volume, particularly in the vicinity of 3% by volume. It was. Moreover, it can be seen from Table 1 and FIG. 2 that the suppression of gas generation was good when the FEC content (volume ratio) to PC was in the range of 4 to 12%, particularly around 6%.

<Example 2-1>
As an electrolytic solution, 0.1 mol / l of 1,3-propane sultone was added to a solvent constituted by PC / TFETFPE / TTFEP = 38/20/40 (volume ratio), and 0.8 mol / l of lithium salt LiPF ₆ was added. . Furthermore, 3,3,3-trifluoropropylene carbonate (FPC), which is a fluorinated cyclic carbonate, was added to 2% by volume. A configuration other than the electrolytic solution was the same as in Example 1-1. A lithium secondary battery was produced, and the amount of gas generated was measured after 300 cycles of 45 ° C. charge / discharge cycles.

<Example 2-2>
The composition of the solvent of the electrolytic solution was changed to PC / TFETFPE / TTFEP = 30/20/40 (volume ratio) instead of PC / TFETFPE / TTFEP = 38/20/40 (volume ratio), and FPC was changed to 2% by volume. A lithium secondary battery was prepared in the same manner as in Example 2-1 except that the amount was 10 vol%, and the amount of gas generated was measured and found to be 0.42 cc.

<Comparative Example A>
A lithium secondary battery was produced in the same manner as in Example 2-1, except that the composition of the solvent of the electrolytic solution was PC / TFETFPE / TTFEP = 40/20/40, and FPC was not added. When the amount was measured, it was 0.72 cc.

  In Example 2-1 and Example 2-2, gas generation was suppressed by the addition of FPC. The content of FPC in the electrolyte solution seems to have an optimum amount in the vicinity of 2% by volume. Moreover, it is thought that gas generation can be satisfactorily suppressed when the content ratio (volume ratio) of FPC to PC is in the vicinity of 5% to 33%.

<Example 3-1>
Except that the composition of the solvent of the electrolytic solution was PC / TFET FPE / DMC = 30/70/1, and FEC was added so that the volume ratio was 2 in the above solvent composition ratio, the same as in Example 1-1. A secondary battery was prepared, and the amount of gas generated after 300 cycles of 45 ° C. charge / discharge cycle was measured to be 0.32 cc.

<Example 3-2>
Example 1-1, except that the composition of the solvent of the electrolytic solution was PC / TFETFPE / TTFEP / DMC = 30/50/20/1, and FEC was added so that the volume ratio was 2 in the solvent composition ratio. A lithium secondary battery was prepared, and the amount of gas generated after 300 cycles of 45 ° C. charge / discharge cycles was measured to be 0.17 cc.

  According to the comparison between Example 3-1 and Example 3-2, the amount of gas generation is smaller when TTFEP is added, and the gas generation suppression effect is further obtained by mixing the fluorine-containing phosphate ester. It was. It can be said that the effect of suppressing the generation of gas is good when the content (volume ratio) of FEC to PC is around 7%. Further, when 2% by volume and 3% by volume of FEC were compared, the amount of gas was 2% by volume of FEC, and the effect of suppressing gas generation was better in the vicinity of 2% by volume with respect to the electrolyte.

<Example 4-1>
Except that the composition of the solvent of the electrolytic solution was PC / TFETFPE / TTFEP / DMC = 30/20/50/3 and FEC was added so that the volume ratio was 3 in the above solvent composition, the same as Example 1-1. A lithium secondary battery was produced, and the amount of gas generated after 50 cycles of 45 ° C. charge / discharge cycles was 0.25 cc.

  In addition, the same lithium secondary battery as in this example was manufactured, charged at 45 ° C. with a constant current of 50 mA to 4.75 V, charged with constant voltage for 2.5 hours, and then discharged to 3.0 V. It was. After charging again under the same conditions, the battery was discharged at 50 mA at 25 mA to 3.0 V. The discharge capacity at this time was measured and found to be 56 mAh.

<Example 4-2>
Example 1-1 except that the composition of the solvent of the electrolytic solution was EC / PC / TFETFPE / TTFEP / DMC = 10/20/20/50/3, and FEC was added so that the volume ratio was 3 in the solvent composition. A lithium secondary battery was produced in the same manner as described above, and the gas generation amount was measured after 50 cycles of 45 ° C. charge / discharge cycles.

  The same lithium secondary battery as in this example was produced, and the discharge capacity at 25 ° C. was measured in the same manner as in Example 4-1. The result was 55 mAh.

実施例４−１および実施例４−２のいずれにおいてもガス発生が抑制されている。電解液に、より多くＰＣを含む実施例４−１は、ガス発生がより抑制されており、かつ、電池容量もＰＣの一部をＥＣに置き換えた実施例４−２と同等以上であった。

Gas generation is suppressed in both Example 4-1 and Example 4-2. In Example 4-1, which contained more PC in the electrolyte, gas generation was further suppressed, and the battery capacity was also equal to or greater than Example 4-2 in which a part of the PC was replaced with EC. .

  The comparative example of the solvent composition which does not contain propylene carbonate is shown below.

<Comparative Example B-1>
A lithium secondary battery was fabricated in the same manner as in Example 1-1 except that the composition of the solvent of the electrolytic solution was FEC / TFETFPE / TTFEP = 30/40/30. The resistance of the electrode increased and the battery operated. I did not.

<Comparative Example B-2>
When a lithium secondary battery was produced in the same manner as in Example 1-1 except that the composition of the solvent of the electrolytic solution was FEC / TFET FPE = 30/70, the resistance of the electrode increased and the battery did not operate.

<Comparative Example B-3>
A lithium secondary battery was produced in the same manner as in Example 1-1 except that the composition of the solvent of the electrolytic solution was FEC / TTFEP = 30/70. As a result, the resistance of the electrode increased and the battery did not operate.

<Comparative Example C>
A lithium secondary battery was produced in the same manner as in Example 1-1 except that the composition of the solvent of the electrolytic solution was EC / FEC / TFETFPE = 30/20/50, and gas was generated after 50 cycles of 45 ° C. charge / discharge cycles. When the amount was measured, it was 1.73 cc.

比較例Ｂ−１〜Ｂ−３においては、ＰＣを含まない電解溶媒の組成とした場合、電極の抵抗が増大し電池が動作しない結果となった。また、比較例Ｃにおいて、ＰＣを含まずにＥＣを含む電解溶媒の組成とした場合はガス発生量が上記の各実施例よりも多い結果となった。

In Comparative Examples B-1 to B-3, when the composition of the electrolytic solvent does not include PC, the resistance of the electrode increases and the battery does not operate. Further, in Comparative Example C, when the composition of the electrolytic solvent containing EC without including PC was used, the gas generation amount was larger than that in each of the above Examples.

  As described above, according to this embodiment, it is possible to obtain a lithium secondary battery in which good characteristics at low temperatures can be expected and gas generation is suppressed.

  The lithium secondary battery of the present embodiment is a secondary battery in which good characteristics at low temperatures can be expected and gas generation is suppressed, and all industrial fields that require a power source, and transportation, storage, and storage of electrical energy It can be used in industrial fields related to supply. Specifically, it can be used for a power source of a mobile device, a power source of a moving / transport medium, a backup power source, a solar power generation, a wind power generation, and a power storage facility for storing power generated by the power generation.

DESCRIPTION OF SYMBOLS 1 Positive electrode active material layer 2 Negative electrode active material layer 3 Positive electrode collector 4 Negative electrode collector 5 Separator 6 Laminate exterior 7 Laminate exterior 8 Negative electrode tab 9 Positive electrode tab

Claims (19)

A lithium ion secondary battery having a positive electrode and a negative electrode capable of occluding and releasing lithium, and a non-aqueous electrolyte containing lithium ions,
The non-aqueous electrolyte is propylene carbonate,
A fluorinated cyclic carbonate represented by the general formula (1), and
Containing one or more selected from fluorine-containing phosphate esters and fluorinated chain ethers,
The content of the propylene carbonate is 1% by volume to 50% by volume in the nonaqueous electrolytic solvent, and the content of the fluorinated cyclic carbonate is 0.1% by volume to 10% by volume in the nonaqueous electrolytic solvent. A lithium ion secondary battery characterized by the above.

[In the formula (1), A to D are each independently a hydrogen atom, a fluorine atom, or a substituted or unsubstituted alkyl group, and at least one of A to D is a fluorine atom or a fluorine-containing alkyl group. is there. ]   The lithium ion secondary battery according to claim 1, wherein the content of propylene carbonate in the nonaqueous electrolytic solvent is 5% by volume or more.   The lithium ion secondary battery according to claim 1 or 2, wherein the content of propylene carbonate in the nonaqueous electrolytic solvent is 40% by volume or less.   The lithium ion secondary battery according to any one of claims 1 to 3, wherein the content of propylene carbonate in the nonaqueous electrolytic solvent is 30% by volume or less.   5. The lithium ion secondary battery according to claim 1, wherein the content of the fluorinated cyclic carbonate in the nonaqueous electrolytic solvent is 1% by volume or more.   The lithium ion secondary battery according to any one of claims 1 to 5, wherein a content of the fluorinated cyclic carbonate in the nonaqueous electrolytic solvent is 2% by volume or more.   The lithium ion secondary battery according to any one of claims 1 to 6, wherein a content of the fluorinated cyclic carbonate in a nonaqueous electrolytic solvent is 5% by volume or less.   The lithium ion secondary battery according to any one of claims 1 to 7, wherein a content ratio of the fluorinated cyclic carbonate to propylene carbonate is 2% by volume or more and 40% by volume or less.   The lithium ion secondary battery according to any one of claims 1 to 8, wherein a content of the fluorinated cyclic carbonate with respect to propylene carbonate is 20% by volume or less.   The lithium ion secondary battery according to any one of claims 1 to 9, wherein a content ratio of the fluorinated cyclic carbonate to propylene carbonate is 4% by volume or more.   The fluorinated cyclic carbonate is at least one selected from the group consisting of compounds having a structure in which some or all of the hydrogen atoms of ethylene carbonate, propylene carbonate or butylene carbonate are substituted with fluorine atoms. The lithium ion secondary battery of any one of Claims 1-10.   The lithium ion secondary battery according to claim 11, wherein the fluorinated cyclic carbonate includes at least one selected from fluoroethylene carbonate and fluoropropylene carbonate. The non-aqueous electrolyte secondary battery according to any one of claims 1 to 12, wherein the fluorinated chain ether is represented by the following formula (2).
_{C n H 2n + 1-l} F l -O-C m H 2m + 1-k F k (2)
[In the formula (2), n is 1, 2, 3, 4, 5 or 6, m is 1, 2, 3 or 4, l is any integer from 0 to 2n + 1, k Is any integer from 0 to 2m + 1, and at least one of l and k is an integer of 1 or more. ] The lithium ion secondary battery according to any one of claims 1 to 13, wherein the fluorine-containing phosphate ester is represented by the following formula (3).

[In Formula (3), R ¹ , R ² and R ³ each independently represents an alkyl group or a fluorine-containing alkyl group, and at least one of R ¹ , R ² and R ³ is a fluorine-containing alkyl group. ] The lithium ion secondary battery according to any one of claims 1 to 14, wherein the positive electrode active material contained in the positive electrode contains a lithium manganese composite oxide represented by the following formula (4).
_{Li a (M x Mn 2-} x-y Y y) (O 4-w Z w) (4)
(In the formula, 0 ≦ x ≦ 1.2, 0 ≦ y, x + y <2, 0 ≦ a ≦ 1.2, and 0 ≦ w ≦ 1. M is made of Co, Ni, Fe, Cr, and Cu. At least one selected from the group, Y is at least one selected from the group consisting of Li, B, Na, Al, Mg, Ti, Si, K and Ca, and Z is from the group consisting of F and Cl At least one kind selected.)   The lithium ion secondary battery according to claim 15, wherein the lithium manganese composite oxide contains at least Ni as M. The positive electrode active material contained in the positive electrode contains at least one lithium metal composite oxide represented by the following formula (5) or (6). Lithium ion secondary battery.
LiMPO ₄ (5)
[In formula (5), M is at least one of Co and Ni. ]
_{Li (Li x M 1-x} -z Mn z) O 2 (6)
[In Formula (6), 0 ≦ x <0.3, 0.3 ≦ z ≦ 0.7, M is at least one of Co and Ni]   18. The lithium ion secondary battery according to claim 1, further comprising: an outer package that includes the positive electrode, the negative electrode, and the non-aqueous electrolyte, and the outer package is made of an aluminum laminate. . A method for producing a lithium ion secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte,
Disposing the positive electrode and the negative electrode opposite to each other via a separator;
A step of accommodating the positive electrode and the negative electrode arranged in a facing manner together with a nonaqueous electrolyte in an exterior body; and
A step of sealing the outer package, wherein the non-aqueous electrolyte is propylene carbonate,
A fluorinated cyclic carbonate represented by the general formula (7), and
Containing one or more selected from fluorine-containing phosphate esters and fluorinated chain ethers,
The content of the propylene carbonate is 1% by volume to 50% by volume in the nonaqueous electrolytic solvent, and the content of the fluorinated cyclic carbonate is 0.1% by volume to 10% by volume in the nonaqueous electrolytic solvent. A method for producing a lithium ion secondary battery.

[In the formula (7), A to D are each independently a hydrogen atom, a fluorine atom, or a substituted or unsubstituted alkyl group, and at least one of A to D is a fluorine atom or a fluorine-containing alkyl group. is there. ]

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