JP4569128B2 - Non-aqueous electrolyte for lithium ion secondary battery and lithium ion secondary battery - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte for a lithium ion secondary battery and a lithium ion secondary battery. Specifically, a non-aqueous electrolyte solution for a lithium ion secondary battery that provides a lithium ion secondary battery with high capacity, excellent storage characteristics and cycle characteristics by including a specific additive, and this non-aqueous electrolyte solution. The present invention relates to the lithium ion secondary battery used.

  With the recent reduction in weight and size of electrical products, development of lithium ion secondary batteries having high energy density is in progress. In addition, with the expansion of the application field of lithium ion secondary batteries, improvement of battery characteristics is also demanded.

  As a negative electrode of a lithium ion secondary battery, metallic lithium, a lithium alloy, a metal compound capable of inserting and extracting lithium (metal simple substance, oxide, etc.) and a carbonaceous material are used. In particular, as a carbonaceous material, for example, a nonaqueous electrolyte secondary battery using a carbonaceous material capable of inserting and extracting lithium such as coke, artificial graphite, and natural graphite has been proposed. In such a non-aqueous electrolyte secondary battery, since lithium does not exist in a metal state, dendrite formation is suppressed, and battery life and safety can be improved. In particular, non-aqueous electrolyte secondary batteries using graphite-based carbonaceous materials such as artificial graphite and natural graphite are attracting attention as meeting the demand for higher capacity.

  In lithium ion secondary batteries using the above carbonaceous material for the negative electrode, cyclic carbonates such as propylene carbonate and ethylene carbonate are usually widely used as high-dielectric constant solvents for non-aqueous electrolytes, especially non-graphite-based materials such as coke. In a non-aqueous electrolyte secondary battery using a carbonaceous material, a solvent containing propylene carbonate is suitably used. However, in a non-aqueous electrolyte secondary battery using a graphite-based carbonaceous material alone or mixed with another negative electrode material capable of inserting and extracting lithium, propylene carbonate is added to the non-aqueous electrolyte. When the solvent is used, the decomposition reaction of propylene carbonate proceeds vigorously on the electrode surface during charging, and smooth insertion and extraction of lithium into the graphite-based carbonaceous negative electrode becomes impossible. On the other hand, since ethylene carbonate has little such decomposition, ethylene carbonate is frequently used as a high dielectric constant solvent for an electrolyte in nonaqueous electrolyte secondary batteries using a graphite-based carbonaceous negative electrode.

  However, even when ethylene carbonate is used as the main solvent for the non-aqueous electrolyte solution, the electrolyte solution decomposes on the electrode surface during the charge / discharge process, so that the charge / discharge efficiency decreases, the cycle characteristics decrease, the battery internal pressure increases due to gas generation, etc. There was a problem.

Therefore, electrolytic solutions containing various additives have been proposed in order to improve the characteristics of non-aqueous electrolyte secondary batteries. For example, in order to suppress the decomposition of the electrolyte solution of a non-aqueous electrolyte battery using a graphite-based negative electrode, the electrolyte solution containing vinylene carbonate and its derivative (Patent Document 1) and the side chain has a nonconjugated unsaturated bond. An electrolytic solution containing an ethylene carbonate derivative (Patent Document 2) has been proposed. In the electrolytic solution containing these compounds, the compound is reduced and decomposed on the negative electrode surface to form a film, and the excessive decomposition of the electrolytic solution is suppressed by this film.
JP-A-8-45545 Japanese Patent Laid-Open No. 2000-40526

  The compounds used in Patent Documents 1 and 2 are not always satisfactory in terms of storage characteristics under a high temperature environment of 80 ° C. or higher. In addition, the vinylene carbonate compound easily reacts with the positive electrode material in a charged state, and the storage characteristics tend to be further lowered as the addition amount increases.

  The present invention has been made in view of the above-mentioned conventional problems, minimizing the decomposition of the non-aqueous electrolyte of the non-aqueous electrolyte secondary battery, high charge and discharge efficiency, storage characteristics even at high temperatures, An object is to provide a non-aqueous electrolyte secondary battery with high energy density and excellent cycle characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have minimized the decomposition of the electrolyte by using a specific sulfite compound as an additive for the non-aqueous electrolyte for a lithium ion secondary battery. It has been found that the charge / discharge efficiency can be suppressed and storage characteristics and cycle characteristics can be improved, and the present invention has been completed.

That is, the gist of the present invention is that in a non-aqueous electrolyte for a lithium ion secondary battery containing an electrolyte and a non-aqueous solvent, at least one sulfite compound represented by the following general formula (I) (however, 4-isopropyl -5,5-dimethyl-1,3,2-dioxathian-2-oxide and 5-methoxymethyl-5-methyl-1,3,2-dioxathian-2-oxide), and the sulfite compound content of the lies in the non-aqueous electrolyte solution for a 0.005 to 7 wt.% der Ru lithium ion secondary battery with respect to the total weight of the nonaqueous electrolytic solution.

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆は、それぞれ独立して、下記のいずれかである。
水素原子、ハロゲン原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロヘキシル基、ビニル基、アリル基、及びフェニル基）

_{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6 are each independently either lower SL.
Water MotoHara child, Ha androgenic atom, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, a cyclohexyl group, a vinyl group, an allyl group, And phenyl group )

  Another gist of the present invention is that a lithium ion secondary battery using the non-aqueous electrolyte for a lithium ion secondary battery of the present invention, that is, metal lithium, lithium alloy or lithium is occluded and released. In a non-aqueous secondary battery comprising a negative electrode including a material capable of absorbing, a positive electrode including a material capable of occluding and releasing lithium, and a non-aqueous electrolyte obtained by dissolving a lithium salt in a non-aqueous solvent The non-aqueous electrolyte is in the lithium ion secondary battery which is the non-aqueous electrolyte of the present invention.

  Although the details of the mechanism of action according to the present invention are not clear, by adding the specific sulfite compound as an additive, the decomposition of the solvent of the non-aqueous electrolyte solution during high-temperature storage is suppressed, thereby the battery after high-temperature storage It is considered that the characteristics can be improved.

  In the present invention, the content of the sulfite compound is preferably 0.005 to 5% by weight with respect to the total weight of the non-aqueous electrolyte, and the sulfite compound is particularly trimethylene glycol sulfite, or Neopentyl glycol sulfite is preferred.

  In the lithium ion secondary battery of the present invention, the negative electrode contains a carbon material having a d value of 0.335 to 0.34 nm on the lattice plane (002) plane in X-ray diffraction, Si, Sn, Ge, and Those containing an element selected from the group consisting of Al, or those containing a metal oxide selected from the group consisting of Si, Sn and Al and those selected from the group consisting of lithium alloys are preferred.

  According to the present invention, a high energy density lithium ion secondary battery having high charge / discharge efficiency and excellent storage characteristics and cycle characteristics even at high temperatures is provided.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following descriptions, and various modifications can be made within the scope of the gist.

  The non-aqueous electrolyte solution for a lithium ion secondary battery of the present invention is a non-aqueous electrolyte solution containing an electrolyte and a non-aqueous solvent, and is at least one sulfite compound represented by the following general formula (I) (provided that 4-isopropyl-5,5-dimethyl-1,3,2-dioxathian-2-oxide and 5-methoxymethyl-5-methyl-1,3,2-dioxathian-2-oxide)) is there.

（式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆は、それぞれ独立して、下記（ｉ）〜（ｉｖ）のいずれかであり、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆のいずれか２個の基が互いに結合して環を形成していても良い。
（ｉ）水素原子
（ｉｉ）ハロゲン原子
（ｉｉｉ）下記の連結基を介して結合している炭素数１〜２０の炭化水素基（この炭化水素基は、水素の一部又は全部がハロゲン原子に置き換えられていても良く、不飽和結合を有していても良い）
エーテル基、カルボニル基、−Ｃ（＝Ｏ）−Ｏ−基、−Ｏ−Ｃ（＝Ｏ）−基、−Ｏ−Ｃ（＝Ｏ）−Ｏ−基、−Ｎ（−Ｒ_７）−基（Ｒ_７は、水素の一部又は全部がハロゲン原子に置き換えられていても良く、不飽和結合を有していても良い炭素数１〜２０の炭化水素基）、−Ｎ（−Ｒ_８）−Ｃ（＝Ｏ）−基（Ｒ_８は、水素の一部又は全部がハロゲン原子に置き換えられていても良く、不飽和結合を有していても良い炭素数１〜２０の炭化水素基）、−Ｎ（−Ｒ_９）−Ｃ（＝Ｏ）−Ｏ−基（Ｒ_９は、水素の一部又は全部がハロゲン原子に置き換えられていても良く、不飽和結合を有していても良い炭素数１〜２０の炭化水素基）、−Ｃ（＝Ｏ）−Ｎ（−Ｒ_１０）−基（Ｒ_１０は、水素の一部又は全部がハロゲン原子に置き換えられていても良く、不飽和結合を有していても良い炭素数１〜２０の炭化水素基）、−Ｏ−Ｃ（＝Ｏ）−Ｎ（−Ｒ_１１）−基（Ｒ_１１は、水素の一部又は全部がハロゲン原子に置き換えられていても良く、不飽和結合を有していても良い炭素数１〜２０の炭化水素基）、スルフィド基、ジスルフィド基、スルホニル基、スルフィニル基、−Ｏ−Ｓ（＝Ｏ）_２−Ｏ−基、−Ｏ−Ｓ（＝Ｏ）−Ｏ−基、−Ｓ（＝Ｏ）_２−Ｏ−基、−Ｏ−Ｓ（＝Ｏ）_２−基、−Ｓ（＝Ｏ）−Ｏ−基、−Ｏ−Ｓ（＝Ｏ）−基
（ｉｖ）水素の一部又は全部が、ハロゲン原子、或いは酸素原子、窒素原子、及び硫黄原子のいずれかを含む官能基で置き換えられていても良く、不飽和結合を有していても良い炭素数１〜２０の炭化水素基）

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently any one of the following (i) to (iv), and R ₁ , R ₂ , R _3: , R ₄ , R ₅ and R ₆ may be bonded to each other to form a ring.
(I) a hydrogen atom (ii) a halogen atom (iii) a hydrocarbon group having 1 to 20 carbon atoms bonded through the following linking group (this hydrocarbon group has a part or all of hydrogen atoms converted to a halogen atom) May be replaced and may have unsaturated bonds)
Ether group, carbonyl group, —C (═O) —O— group, —O—C (═O) — group, —O—C (═O) —O— group, —N (—R ₇ ) — group (R ₇ is a hydrocarbon group having 1 to 20 carbon atoms which may be partially or entirely replaced with a halogen atom and may have an unsaturated bond), —N (—R ₈ ). —C (═O) — group (R ₈ is a hydrocarbon group having 1 to 20 carbon atoms in which part or all of hydrogen may be replaced by a halogen atom and may have an unsaturated bond) , —N (—R ₉ ) —C (═O) —O— group (R ₉ may have part or all of hydrogen replaced with a halogen atom, and may have an unsaturated bond. hydrocarbon group having 1 to 20 carbon atoms), - C (= O) -N (-R 10) - group _{(R 10,} a part of hydrogen or all be replaced by a halogen atom Well, a hydrocarbon group having 1 to 20 carbon atoms that may have an unsaturated bond), - O-C (= O) -N (-R 11) - group _{(R 11,} a part of the hydrogen or All of them may be replaced by halogen atoms, and may have an unsaturated bond (C1-C20 hydrocarbon group), sulfide group, disulfide group, sulfonyl group, sulfinyl group, -O-S ( ═O) ₂ —O— group, —O—S (═O) —O— group, —S (═O) ₂ —O— group, —O—S (═O) ₂ — group, —S (= O) —O— group, —O—S (═O) — group (iv) Part or all of hydrogen is replaced with a halogen atom or a functional group containing any one of an oxygen atom, a nitrogen atom, and a sulfur atom. A hydrocarbon group having 1 to 20 carbon atoms which may have an unsaturated bond)

  First, the sulfite compound contained in the non-aqueous electrolyte of the present invention will be described.

In the general formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R _{6 that} are substituents are each independently any of the following (i) to (iv): Any two groups of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be bonded to each other to form a ring.
(I) a hydrogen atom (ii) a halogen atom (iii) a hydrocarbon group having 1 to 20 carbon atoms bonded through the following linking group (this hydrocarbon group has a part or all of hydrogen atoms converted to a halogen atom) May be replaced and may have unsaturated bonds)
Ether group, carbonyl group, —C (═O) —O— group, —O—C (═O) — group, —O—C (═O) —O— group, —N (—R ₇ ) — group (R ₇ is a hydrocarbon group having 1 to 20 carbon atoms which may be partially or entirely replaced with a halogen atom and may have an unsaturated bond), —N (—R ₈ ). —C (═O) — group (R ₈ is a hydrocarbon group having 1 to 20 carbon atoms in which part or all of hydrogen may be replaced by a halogen atom and may have an unsaturated bond) , —N (—R ₉ ) —C (═O) —O— group (R ₉ may have part or all of hydrogen replaced with a halogen atom, and may have an unsaturated bond. hydrocarbon group having 1 to 20 carbon atoms), - C (= O) -N (-R 10) - group _{(R 10,} a part of hydrogen or all be replaced by a halogen atom Well, a hydrocarbon group having 1 to 20 carbon atoms that may have an unsaturated bond), - O-C (= O) -N (-R 11) - group _{(R 11,} a part of the hydrogen or All of them may be replaced by halogen atoms, and may have an unsaturated bond (C1-C20 hydrocarbon group), sulfide group, disulfide group, sulfonyl group, sulfinyl group, -O-S ( ═O) ₂ —O— group, —O—S (═O) —O— group, —S (═O) ₂ —O— group, —O—S (═O) ₂ — group, —S (= O) —O— group, —O—S (═O) — group (iv) Part or all of hydrogen is replaced with a halogen atom or a functional group containing any one of an oxygen atom, a nitrogen atom, and a sulfur atom. A hydrocarbon group having 1 to 20 carbon atoms which may have an unsaturated bond)

Hereinafter, each case where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are (i) to (iv) will be described in detail.
(I) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be hydrogen atoms.
(Ii) When R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are halogen atoms, examples of the halogen atom include a fluorine atom and a chlorine atom. In particular, the fluorine atom is electrochemically stable. From the viewpoint of sex.
(Iii) A hydrocarbon group having 1 to 20 carbon atoms in which R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are bonded via the following linking group (this hydrocarbon group is hydrogen Part or all of may be replaced by a halogen atom and may have an unsaturated bond)
Ether group, carbonyl group, —C (═O) —O— group, —O—C (═O) — group, —O—C (═O) —O— group, —N (—R ₇ ) — group (R ₇ is a hydrocarbon group having 1 to 20 carbon atoms which may be partially or entirely replaced with a halogen atom and may have an unsaturated bond), —N (—R ₈ ). —C (═O) — group (R ₈ is a hydrocarbon group having 1 to 20 carbon atoms in which part or all of hydrogen may be replaced by a halogen atom and may have an unsaturated bond) , —N (—R ₉ ) —C (═O) —O— group (R ₉ may have part or all of hydrogen replaced with a halogen atom, and may have an unsaturated bond. hydrocarbon group having 1 to 20 carbon atoms), - C (= O) -N (-R 10) - group _{(R 10,} a part of hydrogen or all be replaced by a halogen atom Well, a hydrocarbon group having 1 to 20 carbon atoms that may have an unsaturated bond), - O-C (= O) -N (-R 11) - group _{(R 11,} a part of the hydrogen or All of them may be replaced by halogen atoms, and may have an unsaturated bond (C1-C20 hydrocarbon group), sulfide group, disulfide group, sulfonyl group, sulfinyl group, -O-S ( ═O) ₂ —O— group, —O—S (═O) —O— group, —S (═O) ₂ —O— group, —O—S (═O) ₂ — group, —S (= In the case of O) —O— group and —O—S (═O) — group, R _{1 to} R ₆ hydrocarbon groups having 1 to 20 carbon atoms bonded via the above linking group, and the above linking group the hydrocarbon group having 1 to 20 carbon atoms in _R 7 _{to R 11,} for example a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, iso Til group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, vinyl group, 1-propenyl group, 2-methyl-1-butenyl group, allyl group, 2-butenyl group, 3- Butenyl group, 2-methyl-2-butenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclopentenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, ethynyl group, 1-propynyl group, Examples include propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, benzyl group, phenyl group, tolyl group, xylyl group, 1-naphthyl group, 2-naphthyl group, etc. Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclo A hexyl group, vinyl group, allyl group, and phenyl group are preferred.
The linking group is preferably an ether group from the viewpoint of easy availability of raw materials during production and cost.

  Moreover, the hydrogen atom of these hydrocarbon groups may be substituted with a halogen atom, but in this case, the number of substitution and the substitution position are not particularly limited. Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is particularly preferable from the viewpoint of electrochemical stability. Examples of such halogen-containing hydrocarbon groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a fluorovinyl group, and a fluorophenyl group.

  The molecular weight of the linking group has no particular lower limit, and the upper limit is usually 500 or less, preferably 300 or less.

Specific examples of the group in which the hydrocarbon group is linked via the linking group include the following.
(a) Specific examples of the group via an ether group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, a cyclohexyloxy group, a vinyloxy group, an allyloxy group, an ethynyloxy group, and a benzyloxy group. , A phenoxy group or the like having a carbon number of usually 1 or more and 20 or less, preferably 10 or less.

 (b) Specific examples of the group via the carbonyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, cyclohexylcarbonyl group, acrylic group, 2-vinylacetyl group, ethynylcarbonyl group, benzylcarbonyl group, Examples of the benzoyl group include those having usually 1 or more and 20 or less, preferably 10 or less carbon atoms.

 (c) Specific examples of the group via —C (═O) —O— group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, cyclohexylcarbonyl group, vinyl An oxycarbonyl group, an allyloxycarbonyl group, an ethynyloxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl group and the like having a carbon number of usually 2 or more and 20 or less, preferably 10 or less can be mentioned.

 (d) Specific examples of the group via —O—C (═O) — group include acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, cyclohexylcarbonyloxy group, acryloxy group , 2-vinylacetyloxy group, ethynylcarbonyloxy group, benzylcarbonyloxy group, benzoyloxy group and the like having a carbon number of usually 1 or more and 20 or less, preferably 10 or less.

 (e) Specific examples of the group through the —O—C (═O) —O— group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group, and an isopropyloxycarbonyloxy group. , A cyclohexylcarbonyloxy group, a vinyloxycarbonyloxy group, an allyloxycarbonyloxy group, an ethynyloxycarbonyloxy group, a benzyloxycarbonyloxy group, a phenoxycarbonyloxy group, etc., usually 2 or more, 20 or less, preferably 10 or less. Can be mentioned.

(f) Specific examples of the group via —N (—R ₇ ) — group include dimethylamino group, diethylamino group, di (n-propyl) amino group, diisopropylamino group, dicyclohexylamino group, divinylamino group. Group, diallylamino group, diethynylamino group, dibenzylamino group, diphenylamino group, methylethylamino group, methyl (n-propyl) amino group, methylisopropylamino group, methylcyclohexylamino group, methylvinylamino group, methyl Allylamino group, methylethynylamino group, methylbenzylamino group, methylphenylamino group, ethylphenylamino group, n-propylphenylamino group, isopropylphenylamino group, cyclohexylphenylamino group, phenylvinylamino group, allylphenylamino group , Ethinylph Niruamino group, usually 2 or more carbon atoms such as benzyl phenylamino group, 40 or less, preferably of 20 or less.

(g) Specific examples of the group via —N (—R ₈ ) —C (═O) — group include N-methyl-N- (methylcarbonyl) group, N-methyl-N- (ethyl) Carbonyl) group, N-methyl-N- (n-propylcarbonyl) group, N-methyl-N- (isopropylcarbonyl) group, N-methyl-N- (cyclohexylcarbonyl) group, N-methyl-N- (vinyl) Carbonyl) group, N-methyl-N- (allylcarbonyl) group, N-methyl-N- (ethynylcarbonyl) group, N-methyl-N- (benzylcarbonyl) group, N-methyl-N- (phenylcarbonyl) Group, N-phenyl-N- (methylcarbonyl) group, N-phenyl-N- (ethylcarbonyl) group, N-phenyl-N- (n-propylcarbonyl) group, N-phenyl-N- (isopropylcarbonyl) Group, N-phenyl-N- (cyclohexylcarbonyl) group, N-phenyl-N- (vinylcarbonyl) group, N-phenyl-N- (allylcarbonyl) group, N-phenyl-N- (ethynylcarbonyl) group, A carbon number such as N-phenyl-N- (phenylcarbonyl) group is usually 3 or more and 40 or less, preferably 20 or less.

(h) Specific examples of the group via —N (—R ₉ ) C (═O) —O— group include N-methyl-N- (methoxycarbonyl) group, N-methyl-N— ( Ethoxycarbonyl) group, N-methyl-N- (n-propyloxycarbonyl) group, N-methyl-N- (isopropyloxycarbonyl) group, N-methyl-N- (cyclohexyloxycarbonyl) group, N-methyl- N- (vinyloxycarbonyl) group, N-methyl-N- (allyloxycarbonyl) group, N-methyl-N- (ethynyloxycarbonyl) group, N-methyl-N- (benzyloxycarbonyl) group, N- Methyl-N- (phenoxycarbonyl) group, N-phenyl-N- (methoxycarbonyl) group, N-phenyl-N- (ethoxycarbonyl) group, N-phenyl-N- (n-propyloxy) Carbonyl) group, N-phenyl-N- (isopropyloxycarbonyl) group, N-phenyl-N- (cyclohexyloxycarbonyl) oxy group, N-phenyl-N- (vinyloxycarbonyl) group, N-phenyl-N- Carbon numbers such as (allyloxycarbonyl) group, N-phenyl-N- (ethynyloxycarbonyl) group, N-phenyl-N- (benzyloxycarbonyl) group, N-phenyl-N- (phenoxycarbonyl) group are usually 3 or more and 40 or less, preferably 20 or less.

(i) Specific examples of the group via the —C (═O) —N (—R ₁₀ ) — group include N, N-dimethylaminocarbonyl group, N, N-diethylaminocarbonyl group, N, N -Di (n-propyl) aminocarbonyl group, N, N-diisopropylaminocarbonyl group, N, N-dicyclohexylaminocarbonyl group, N, N-divinylaminocarbonyl group, N, N-diallylaminocarbonyl group, N, N -Diethynylaminocarbonyl group, N, N-dibenzylaminocarbonyl group, N, N-diphenylaminocarbonyl group, N-ethyl-N-methylaminocarbonyl group, N- (n-propyl) -N-methylaminocarbonyl Group, N-isopropyl-N-methylaminocarbonyl group, N-cyclohexyl-N-methylaminocarbonyl group, N-vinyl-N- Tilaminocarbonyl group, N-allyl-N-methylaminocarbonyl group, N-ethynyl-N-methylaminocarbonyl group, N-benzyl-N-methylaminocarbonyl group, N-methyl-N-phenylaminocarbonyl group, N -Ethyl-N-phenylaminocarbonyl group, N- (n-propyl) -N-phenylaminocarbonyl group, N-isopropyl-N-phenylaminocarbonyl group, N-cyclohexyl-N-phenylaminocarbonyl group, N-phenyl -N-vinylaminocarbonyl group, N-allyl-N-phenylaminocarbonyl group, N-ethynyl-N-phenylaminocarbonyl group, N-benzyl-N-phenylaminocarbonyl group and the like usually have 3 or more carbon atoms, 40 Hereinafter, preferably 20 or less.

(j) Specific examples of the group through the —O—C (═O) —N (—R ₁₁ ) — group include N, N-dimethylaminocarbonyloxy group and N, N-diethylaminocarbonyloxy group. N, N-di (n-propyl) aminocarbonyloxy group, N, N-diisopropylaminocarbonyloxy group, N, N-dicyclohexylaminocarbonyloxy group, N, N-divinylaminocarbonyloxy group, N, N- Diallylaminocarbonyloxy group, N, N-diethynylaminocarbonyloxy group, N, N-dibenzylaminocarbonyloxy group, N, N-diphenylaminocarbonyloxy group, N-ethyl-N-methylaminocarbonyloxy group, N- (n-propyl) -N-methylaminocarbonyloxy group, N-isopropyl-N-methylaminocarb Nyloxy group, N-cyclohexyl-N-methylaminocarbonyloxy group, N-vinyl-N-methylaminocarbonyloxy group, N-allyl-N-methylaminocarbonyloxy group, N-ethynyl-N-methylaminocarbonyloxy group N-benzyl-N-methylaminocarbonyloxy group, N-methyl-N-phenylaminocarbonyloxy group, N-ethyl-N-phenylaminocarbonyloxy group, N- (n-propyl) -N-phenylaminocarbonyl Oxy group, N-isopropyl-N-phenylaminocarbonyloxy group, N-cyclohexyl-N-phenylaminocarbonyloxy group, N-phenyl-N-vinylaminocarbonyloxy group, N-allyl-N-phenylaminocarbonyloxy group N-ethynyl-N-pheny Aminocarbonyl group, carbon atoms, such as N- benzyl -N- phenylaminocarbonyl group is usually 3 or more, 40 or less, preferably of 20 or less.

 (k) Specific examples of the group via the sulfide group include a methylthioether group, an ethylthioether group, an n-propylthioether group, an isopropylthioether group, a cyclohexylthioether group, a vinylthioether group, an allylthioether group, and an ethynylthioether group. , A benzylthioether group, a phenylthioether group and the like having a carbon number of usually 1 or more and 20 or less, preferably 10 or less.

 (l) Specific examples of the group via the disulfide group include methyl dithioether group, ethyl dithioether group, n-propyl dithioether group, isopropyl dithioether group, cyclohexyl dithioether group, vinyl dithioether group, allyl group Examples of the dithioether group include an ethynyl dithioether group, a benzyl dithioether group, and a phenyl dithioether group that usually have 1 or more and 20 or less, preferably 10 or less carbon atoms.

 (m) Specific examples of the group via the sulfonyl group include a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an isopropylsulfonyl group, a cyclohexylsulfonyl group, a vinylsulfonyl group, an allylsulfonyl group, and an ethynylsulfonyl group. , Benzylsulfonyl group, phenylsulfonyl group and the like, and those having usually 1 or more and 20 or less, preferably 10 or less carbon atoms.

 (n) Specific examples of the group via sulfinyl group include methanesulfinyl group, ethanesulfinyl group, n-propanesulfinyl group, isopropylsulfinyl group, cyclohexylsulfinyl group, vinylsulfinyl group, allylsulfinyl group, ethynylsulfinyl group , Benzylsulfinyl group, phenylsulfinyl group and the like, and those having usually 1 to 20, preferably 10 or less carbon atoms.

(o) Specific examples of the group via —O—S (═O) ₂ — group include a methanesulfonyloxy group, an ethanesulfonyloxy group, an n-propanesulfonyloxy group, an isopropylsulfonyloxy group, and a cyclohexylsulfonyl group. An oxy group, a vinyl sulfonyloxy group, an allyl sulfonyloxy group, an ethynyl sulfonyloxy group, a benzyl sulfonyl group oxy, a phenyl sulfonyloxy group, etc. whose carbon number is 1 or more normally 20 or less, Preferably it is 10 or less is mentioned.

 (p) Specific examples of the group via —O—S (═O) —O— group include a methoxysulfinyloxy group, an ethoxysulfinyloxy group, an n-propyloxysulfinyloxy group, and an isopropyloxysulfinyloxy group. A cyclohexyloxysulfinyloxy group, a vinyloxysulfinyloxy group, an allyloxysulfinyloxy group, an ethynyloxysulfinyloxy group, a benzyloxysulfinyloxy group, a phenoxysulfinyloxy group, and the like. The following are mentioned.

(q) Specific examples of the group via —S (═O) ₂ —O— group include a methoxysulfonyl group, an ethoxysulfonyl group, an n-propyloxysulfonyl group, an isopropyloxysulfonyl group, and a cyclohexyloxysulfonyl group. , A vinyloxysulfonyl group, an allyloxysulfonyl group, an ethynyloxysulfonyl group, a benzyloxysulfonyl group, a phenoxysulfonyl group and the like, which have usually 1 to 20, preferably 10 or less.

(r) Specific examples of the group via —O—S (═O) ₂ —O— group include methoxysulfonyloxy group, ethoxysulfonyloxy group, n-propyloxysulfonyloxy group, isopropyloxysulfonyloxy Group, cyclohexyloxysulfonyloxy group, vinyloxysulfonyloxy group, allyloxysulfonyloxy group, ethynyloxysulfonyloxy group, benzyloxysulfonyloxy group, phenoxysulfonyloxy group and the like usually have 1 to 20 carbon atoms, preferably 10 or less are mentioned.

(s) Specific examples of the group via —S (═O) —O— group include methoxysulfinyl group, ethoxysulfinyl group, n-propyloxysulfinyl group, isopropyloxysulfinyl group, cyclohexyloxysulfinyl group, Examples thereof include a vinyloxysulfinyl group, an allyloxysulfinyl group, an ethynyloxysulfinyl group, a benzyloxysulfinyl group, a phenoxysulfinyl group and the like whose carbon number is usually 1 or more and 20 or less, preferably 10 or less.

(t) Specific examples of the group via —O—S (═O) — group include methanesulfinyloxy group, ethanesulfinyloxy group, n-propanesulfinyloxy group, isopropylsulfinyloxy group, cyclohexylsulfinyloxy group. Group, vinyl sulfinyloxy group, allyl sulfinyloxy group, ethynyl sulfinyloxy group, benzyl sulfinyloxy group, phenylsulfinyloxy group and the like are usually 1 or more, 20 or less, preferably 10 or less.

In (iii), there is no particular lower limit of the molecular weight of the substituents R _{1 to} R ₆ as a whole, and the upper limit is usually 1000 or less, preferably 500 or less.

(Iv) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are functional groups in which part or all of hydrogen contains any of a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. In the case of a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with an unsaturated bond, examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, vinyl group, 1-propenyl group, 2-methyl-1-butenyl group, allyl group 2-butenyl group, 3-butenyl group, 2-methyl-2-butenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclopentenyl group, 2-cyclohexenyl group, 3-cyclohexyl Hexenyl group, ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, benzyl group, phenyl group, tolyl group, xylyl group, 1-naphthyl group, 2-naphthyl group In particular, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclohexyl group, vinyl group, allyl group, phenyl, etc. Groups are preferred.

  Moreover, when the hydrogen atom of these hydrocarbon groups is substituted with a halogen atom, the number of substitution and the substitution position are not particularly limited. Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is particularly preferable from the viewpoint of electrochemical stability. Examples of such halogen-containing hydrocarbon groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a fluorovinyl group, and a fluorophenyl group.

The said C1-C20 hydrocarbon group may be each independently substituted with the functional group containing an oxygen atom, a nitrogen atom, and a sulfur atom. Here, examples of the functional group containing an oxygen atom include an ether group, a carbonyl group, a —C (═O) —O— group, a —O—C (═O) — group, and —O—C (═O) —O. -What has group etc. are mentioned. As the functional group containing a nitrogen atom, a —N (—R ₁₂ ) — group (R ₁₂ may have part or all of hydrogen replaced with a halogen atom, and may have an unsaturated bond. A hydrocarbon group having 1 to 20 carbon atoms), a —N (—R ₁₃ ) —C (═O) — group (R ₁₃ may be partially or entirely substituted with a halogen atom, and unsaturated. A hydrocarbon group having 1 to 20 carbon atoms which may have a bond), —N (—R ₁₄ ) —C (═O) —O— group (R ₁₄ is a part or all of hydrogen being a halogen atom) Or a C 1-20 hydrocarbon group which may have an unsaturated bond), -C (= O) -N (-R ₁₅ )-group (R ₁₅ is hydrogen A carbon atom having 1 to 20 carbon atoms, which may be partially or wholly substituted with a halogen atom and may have an unsaturated bond Hydrogen group), - O-C (= O) -N (-R 16) - group _{(R 16,} a part of hydrogen or all may be substituted by a halogen atom, have an unsaturated bond Or a hydrocarbon group having 1 to 20 carbon atoms). Examples of the functional group containing a sulfur atom include a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, an —O—S (═O) ₂ —O— group, an —O—S (═O) —O— group, and —S. Those having (═O) ₂ —O— group, —O—S (═O) ₂ — group, —S (═O) —O— group, —O—S (═O) — group and the like can be mentioned. . _As the hydrocarbon group and its halogen substituents of 1 to 20 carbon atoms of R 12 _{to R 16,} those exemplified as the hydrocarbon group and its halogen substituents of 1 to 20 carbon atoms of R 7 _{to R 11} Can be mentioned.

Specific examples of such a functional group include those exemplified in (a) to (t) mentioned as specific examples of R _{1 to} R ₆ in the description of (iii).
Among these functional groups, oxygen-containing functional groups are preferable, and those having an ether group are particularly preferable from the viewpoint of availability of raw materials and cost.

In (iv), there is no particular lower limit on the molecular weight of the substituents R _{1 to} R ₆ as a whole, and the upper limit is usually 1000 or less, preferably 500 or less.

In the general formula (I), any one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be bonded to each other to form a ring. In this case, the bonding mode with the heterocyclic ring represented by the general formula (I) may be either a spiro type or a condensed ring type, and the bonding position and the number thereof are not particularly limited. Moreover, when the coupling | bonding mode with the heterocyclic ring shown by the said general formula (I) is a condensed form, the formed ring may be an aromatic ring.

  Examples of this ring structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a tetrahydrofuran ring, a pyrrolidine ring, a benzene ring, a furan ring, a pyrrole ring, and a thiophene ring.

Further, in the general formula (I), any one of R _{1 to} R ₁₆ may be bonded to each other to form a ring.

Specific examples of the sulfite compound represented by the general formula (I) include
(I) trimethylene glycol sulfite (ii) 5-fluoro-1,3,2-dioxathian-2-oxide (iii) 4-acetyl-1,3,2-dioxathian-2-oxide, 5-methoxy-1 , 3,2-dioxathian-2-oxide (iv) 1,3-butanediol sulfite, 1,3-pentanediol sulfite, 2,4-pentanediol sulfite, neopentyl glycol sulfite, 4,4- Dimethyl-1,3,2-dioxathian-2-oxide, 4-vinyl-1,3,2-dioxathian-2-oxide, 4-allyl-1,3,2-dioxathian-2-oxide, 4-phenyl- 1,3,2-dioxathian-2-oxide, 4-methoxymethyl-1,3,2-dioxathian-2-oxide, etc. Examples thereof include trimethylene glycol sulfite, 1,3-butanediol sulfite, 1,3-pentanediol sulfite, 2,4-pentanediol sulfite, and neopentyl glycol sulfite. Among these, trimethylene glycol sulfite and neopentyl glycol sulfite are particularly preferable from the viewpoints of availability of raw materials when manufacturing these compounds and cost.

  The molecular weight of the sulfite compound represented by the general formula (I) is 122 or more as a lower limit and usually 1200 or less, preferably 600 or less as an upper limit. If the molecular weight of the sulfite compound is too large, the solubility tends to deteriorate.

  These sulfite compounds may be used alone or in combination of two or more.

  The content of the sulfite compound represented by the general formula (I) is usually 0.005% by weight or more, preferably 0.1% by weight or more, and usually 10% by weight or less based on the total weight of the non-aqueous electrolyte solution. It is preferably 5% by weight or less. When the above lower limit is not reached, a film at the negative electrode interface is not sufficiently formed, and various characteristics of the battery are likely to be deteriorated. When the upper limit is exceeded, a film at the negative electrode interface is excessively formed, thereby It becomes easy to deteriorate the characteristics.

  The sulfite compound represented by the general formula (I) can be used in combination of two or more, so long as it does not exceed the scope of the effect of the present invention. The total amount of the phyto compound is usually 0.005% by weight or more, preferably 0.1% by weight or more, usually 10% by weight or less, preferably 5% by weight or less based on the total weight of the non-aqueous electrolyte solution. To.

  Next, the nonaqueous solvent used in the present invention will be described.

  There is no restriction | limiting in particular in the kind of nonaqueous solvent used by this invention, Arbitrary nonaqueous solvents can be used. Specific examples include cyclic carbonates such as ethylene carbonate and propylene carbonate, usually 3 or more and 10 or less, preferably 5 or less, such as cyclic carbonates, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. Hereinafter, preferably a cyclic ester such as a chain carbonate having 5 or less, γ-butyrolactone, γ-valerolactone, etc., usually 3 or more, preferably 4 or more, and usually 10 or less, preferably 8 or less, and methyl acetate. In general, a chain ester having 2 or more and 10 or less carbon atoms, preferably 5 or less carbon atoms such as methyl propionate, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, or the like, and usually having 3 or more carbon atoms, preferably 4 or more carbon atoms. A cyclic ether having usually 10 or less carbon atoms, preferably 8 or less A chain ether having usually 3 or more carbon atoms, preferably 4 or more and usually 10 or less carbon atoms, preferably 8 or less, and a sulfur-containing organic solvent such as sulfolane or diethylsulfone, such as dimethoxyethane or dimethoxymethane. Can be mentioned. These non-aqueous solvents may be used alone or in combination of two or more in any combination and ratio.

As a non-aqueous solvent,
(1) Combination of cyclic carbonate and chain carbonate
(2) Combination of cyclic carbonate and cyclic ester
(3) Combination of cyclic ester and chain ester
(4) A combination of a cyclic carbonate and a cyclic carbonate is preferable from the viewpoint of dissociation of lithium salt as an electrolyte and electrical conductivity. Preferably, the combination is mixed so that 70% by volume or more of the whole nonaqueous solvent is obtained. The non-aqueous solvent is preferable from the viewpoint of improving overall battery performance such as charge / discharge characteristics and battery life.

  Specific examples of the cyclic carbonate, the chain carbonate, the cyclic ester, and the chain ester used in the above combinations (1) to (4) include the following.

[Cyclic carbonate]
Specific examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate and the like. Of these, ethylene carbonate and propylene carbonate are preferable. One of these may be used alone, or a plurality of these may be used in any combination and ratio.

[Chain carbonate]
Specific examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, ethyl methyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate and the like. Of these, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable. One of these may be used alone, or a plurality of these may be used in any combination and ratio.

[Cyclic ester]
Specific examples of the cyclic ester include γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like. Of these, γ-butyrolactone and γ-valerolactone are preferable. One of these may be used alone, or a plurality of these may be used in any combination and ratio.

[Chain esters]
Specific examples of the chain ester include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-propionate. Examples include butyl, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, and n-butyl butyrate. Of these, ethyl acetate, methyl propionate, and ethyl propionate are preferable. One of these may be used alone, or a plurality of these may be used in any combination and ratio.

  In the example (1), the combination of the cyclic carbonate and the chain carbonate is each alone, and contains 10% by volume or more with respect to the total volume of the non-aqueous electrolyte, and the total of these volumes is the non-aqueous electrolyte. A mixed non-aqueous solvent mixed so as to be 70% by volume or more with respect to the total volume is preferable from the viewpoint of improving overall battery performance such as charge / discharge characteristics and battery life.

  The mixed nonaqueous solvent may contain a solvent other than the cyclic carbonate and the chain carbonate as long as the battery performance of the manufactured lithium ion secondary battery is not deteriorated. The ratio of the solvent other than the cyclic carbonate and the chain carbonate in the nonaqueous electrolytic solution is usually 30% by volume or less, preferably 10% by volume or less.

  In the example (2), the combination of the cyclic carbonate and the cyclic ester is a simple substance, and it contains 10% by volume or more with respect to the total volume of the non-aqueous electrolyte, and the content of the cyclic ester is that of the non-aqueous electrolyte. It is preferable that it is 50 volume% or more with respect to the total volume. Moreover, the mixed non-aqueous solvent mixed so that the sum total of those volumes may be 70 volume% or more with respect to a non-aqueous electrolyte is preferable from a viewpoint of improving battery performance in general, such as a charge / discharge characteristic and battery life.

  The mixed non-aqueous solvent may contain a solvent other than the cyclic carbonate and the cyclic ester as long as the battery performance of the manufactured lithium ion secondary battery is not deteriorated. Specific examples thereof include the chain carbonates exemplified above. The proportion of the solvent other than the cyclic carbonate and cyclic ester in the nonaqueous electrolytic solution is usually 30% by volume or less, preferably 10% by volume or less.

  In the example (3), the combination of the cyclic carbonate and the chain ester is each alone, and it contains 10% by volume or more with respect to the total volume of the non-aqueous electrolyte, and the total of these volumes is the non-aqueous electrolyte. A mixed non-aqueous solvent mixed so as to be 70% by volume or more with respect to the total volume is preferable from the viewpoint of improving overall battery performance such as charge / discharge characteristics and battery life.

  The mixed non-aqueous solvent may contain a solvent other than the cyclic carbonate and the chain ester as long as the battery performance of the manufactured lithium ion secondary battery is not deteriorated. The ratio of the solvent other than the cyclic carbonate and the chain ester in the nonaqueous electrolytic solution is usually 30% by volume or less, preferably 10% by volume or less.

  In the combination of cyclic carbonate and cyclic carbonate in the above example (4), each is contained alone, containing 10% by volume or more with respect to the total volume of the non-aqueous electrolyte solution, and the total of these volumes is that of the non-aqueous electrolyte solution. A mixed non-aqueous solvent mixed so as to be 70% by volume or more of the total volume is preferable from the viewpoint of improving overall battery performance such as charge / discharge characteristics and battery life.

  The mixed non-aqueous solvent may contain a solvent other than the cyclic carbonate as long as the battery performance of the manufactured lithium ion secondary battery is not deteriorated. The ratio of the solvent other than the cyclic carbonate in the total volume of the nonaqueous electrolytic solution is usually 30% by volume or less, preferably 10% by volume or less.

  Next, the electrolyte used in the present invention will be described.

The electrolyte is not particularly limited as long as it is a lithium salt, and various electrolytes can be used. Examples of those usually _{used, LiPF 6, LiBF 4, LiClO} 4, LiAsF 6, LiSbF inorganic lithium salt such as _{6, LiCF 3 SO 3, LiN} (CF 3 SO 2) 2, LiN (CF 3 CF 2 Fluorine-containing organic lithium salts such as SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ), LiC (CF ₃ SO ₂ ) ₃ , Li [PF ₅ (CF ₂ CF ₂ CF ₃ )] Li [PF ₄ (CF ₂ CF ₂ CF ₃ ) ₂ ], Li [PF ₃ (CF ₂ CF ₂ CF ₃ ) ₃ ], Li [PF ₃ (CF ₂ CF ₃ ) ₃ ], Li [PF ₅ (CF ₂ CF ₂ CF ₂ CF ₃ )], Li [PF ₄ (CF ₂ CF ₂ CF ₂ CF ₃ ) ₂ ], Li [PF ₃ (CF ₂ CF ₂ CF ₂ CF ₃ ) ₃ ], etc. Lithium fluorofluorophosphate, lithium fluoroalkylborate such as Li [BF ₃ (CF ₃ )], Li [BF ₃ (CF ₂ CF ₃ )], Li [BF ₂ (CF ₂ CF ₃ ) ₂ ], LiB ( _{CF 3 COO) 4, LiB (} OCOCF 2 COO) 2, LiB (OCOC 2 H 4 COO) 2, LiB (C 2 O 4) , and the like. These lithium salts may be used alone or in combination of any number and ratio. Of these, LiPF ₆ and LiBF ₄ are preferably used.

  The concentration of the electrolyte lithium salt in the non-aqueous electrolyte solution is not particularly limited, but the electrolyte lithium salt concentration suitable as the non-aqueous electrolyte solution of the present invention is usually 0.5 mol or more per liter of the non-aqueous electrolyte solution, preferably Is in the range of 0.7 mol or more and usually 2 mol or less, preferably 1.5 mol or less. When the concentration of the electrolyte lithium salt is outside this range, the electrical conductivity of the non-aqueous electrolyte solution of the present invention deteriorates or the viscosity is affected, so that the lithium ion secondary battery obtained by using this electrolyte Performance may be reduced.

  The non-aqueous electrolyte of the present invention includes trioctyl phosphate, polyoxyethylene ethers having a perfluoroalkyl group, perfluoro, in order to improve the coatability with the separator described later in addition to the above non-aqueous solvent and electrolyte. Surfactants such as octane sulfonates may be added in the range of 0.01 to 1% by weight based on the total weight of the non-aqueous solvent.

  Furthermore, in the non-aqueous electrolyte of the present invention, various additives, for example, other film forming agents that are considered to prevent the decomposition of the solvent in the electrode by forming a film on the surface of the electrode, You may mix and use a dehydrating agent, a deoxidizing agent, etc.

  As other film forming agents, it is preferable to use vinylene carbonate compounds, vinyl ethylene carbonate compounds, aryl-substituted carbonates, cyclic carboxylic acid anhydrides, sulfonic acid derivatives, sulfone compounds, five-membered ring or chain sulfite compounds.

  As the vinylene carbonate compound, vinylene carbonate, 4-methyl vinylene carbonate, or the like is used.

  As the vinyl ethylene carbonate compound, 4-vinyl ethylene carbonate, 4-methyl-4-vinyl ethylene carbonate, 5-methyl-4-vinyl ethylene carbonate, or the like is used.

  As the aryl-substituted carbonate, 4-phenylethylene carbonate, methylphenyl carbonate or the like is used.

  As the cyclic carboxylic acid anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, trimellitic anhydride, phthalic anhydride and the like are used. Examples of the sulfonic acid derivative include propane sultone, methyl methanesulfonate, ethyl methanesulfonate, dimethylmethanesulfonate amide, and the like.

  As the sulfone compound, dimethyl sulfone, sulfolane, 3-sulfolene and the like are used.

  Examples of cyclic or chain sulfite compounds include ethylene sulfite, erythritan sulfite, 4-vinylethylene sulfite, 4-isopropyl-5,5-dimethyl-1,3,2-dioxathian-2-oxide, 5- Methoxymethyl-5-methyl-1,3,2-dioxathian-2-oxide, dimethyl sulfite, ethyl methyl sulfite, and diethyl sulfite are used.

  As the film forming agent, vinylene carbonate and 4-vinylethylene carbonate are particularly preferable since the thermal stability of the negative electrode film is improved.

  When these other film-forming agents and at least one sulfite compound represented by the above general formula (I) are mixed and used, a composite film is formed on the negative electrode or the heat of the film The characteristics including the stability may be improved, and the capacity maintenance characteristics and cycle characteristics of the battery may be improved.

  When these other film forming agents are contained in an amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, based on the non-aqueous solvent, the capacity maintenance characteristics and cycle characteristics of the battery are improved.

  In particular, when the non-aqueous electrolyte for a lithium ion secondary battery of the present invention contains a film-forming agent such as vinylene carbonate or 4-vinylethylene carbonate, these film-forming agents and the general formula (I) according to the present invention The content ratio with the sulfite compound represented by the formula is preferably in the range of film forming agent: sulfite compound = 1: 0.005 to 10 (weight ratio).

  Examples of the overcharge inhibitor include benzene derivatives described in JP-A-8-203560, JP-A-7-302614, JP-A-9-50822, JP-A-8-273700, JP-A-9-17447, and the like. Biphenyl and its derivatives described in JP-A-106835, JP-A-9-171840, JP-A-10-32258, JP-A-7-302614, JP-A-11-162512, JP-A-2939469, JP-A-2963898, etc. Partially hydrogenated terphenyl compounds and derivatives thereof described in 2003-100034, JP-A-2003-100345, JP-A-2003-100346, JP-A-2003-115325, etc., JP-A-2003-77536 2-oxazolidone derivatives described in JP-A-9-45369, 10 No. 321258, etc., pyrrole derivatives described in JP-A-7-320778, JP-A-7-302614, etc., aromatic compounds such as aniline derivatives, patent 2983205, etc. And other compounds such as those described in JP-A-2001-15158 can be contained. It is preferable to contain an overcharge inhibitor so that it may become 0.1 to 5 weight% with respect to a non-aqueous solvent.

  Next, the lithium ion secondary battery of the present invention using such a nonaqueous electrolytic solution of the present invention will be described.

  A lithium ion secondary battery according to the present invention includes a negative electrode including a metal lithium, a lithium alloy, or a material capable of inserting and extracting lithium, a positive electrode including a material capable of inserting and extracting lithium, and a lithium salt. And a non-aqueous electrolyte obtained by dissolving in a non-aqueous solvent, wherein the non-aqueous electrolyte for a lithium ion secondary battery according to the present invention described above is used as the non-aqueous electrolyte. .

[Positive electrode and negative electrode]
The active material of the negative electrode constituting the lithium ion secondary battery of the present invention is not particularly limited as long as it contains metallic lithium, a lithium alloy, or a material capable of inserting and extracting lithium. Examples include pyrolysis products of organic substances under various pyrolysis conditions, carbon materials such as artificial graphite and natural graphite, metal oxide materials, and various lithium alloys. Preferably, artificial graphite and purified natural graphite produced by high-temperature heat treatment of graphitizable pitch obtained from various raw materials, or graphite materials obtained by subjecting these graphite to various surface treatments containing pitch are mainly used.

  These graphite materials have a d-value (interlayer distance) of the lattice plane (002) determined by X-ray diffraction by the Gakushin method, which is usually 0.335 nm or more and 0.34 nm or less, preferably 0.337 nm or less. Is desirable.

  The graphite material preferably has an ash content of 1% by weight or less, more preferably 0.5% by weight or less, and most preferably 0.1% by weight or less.

  The crystallite size (Lc) obtained by X-ray diffraction of the above graphite material by the Gakushin method is usually 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more.

  The median diameter of the above graphite material is a median diameter measured by a laser diffraction / scattering method, and is usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, further preferably 7 μm or more, and usually 100 μm or less, preferably It is 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less.

Further, the BET specific surface area of the above graphite material is usually 0.5 m ² / g or more, preferably 0.7 m ² / g or more, more preferably 1.0 m ² / g or more, and further preferably 1.5 m ^2. and a / g or more, and usually 25.0 m ² / g or less, preferably 20.0 m ² / g or less, more preferably 15.0 m ² / g or less, more preferably is less 10.0 m ² / g .

Further, the above graphite material has a peak PA (peak intensity IA) in the range of 1580 to 1620 cm ⁻¹ and a peak PB (peak intensity IB) in the range of 1350 to 1370 cm ⁻¹ in Raman spectrum analysis using an argon ion laser beam. ) of the intensity ratio R = IB / IA is 0 or more and 0.5 or less, the half width of the peak in the range of 1580～1620Cm ^-1 is 26cm ^-1 or less, a half value width of the peak in the range of 1580～1620Cm ^-1 it is 25 cm ^- It is preferably ¹ or less.

  In addition, these carbonaceous materials can be used by mixing a metal compound capable of inserting and extracting lithium. Examples of metal compounds capable of inserting and extracting lithium include compounds containing metals such as Ag, Zn, Al, Ga, In, Si, Ge, Sn, Pb, P, Sb, Bi, Cu, Ni, Sr, and Ba. These metals are used as simple substances, oxides, alloys with lithium, and the like. In the present invention, those containing an element selected from Si, Sn, Ge and Al are preferred, and oxides or lithium alloys of metals selected from Si, Sn and Al are more preferred.

  These negative electrode materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The method for producing a negative electrode using these negative electrode materials is not particularly limited. For example, a negative electrode can be produced by adding a binder, a thickener, a conductive material, a solvent, and the like to the negative electrode material as necessary to form a slurry, which is applied to a substrate of a current collector and dried. it can. In this case, it can be manufactured in the same manner as the positive electrode manufacturing method as described later.

  In addition, the negative electrode material added with a binder or a conductive material is roll-formed as it is to form a sheet electrode, a pellet electrode by compression molding, or deposition, sputtering, plating, etc. on the current collector A thin film of negative electrode material can also be formed.

The active material of the positive electrode constituting the lithium ion secondary battery of the present invention is not particularly limited as long as it is a material capable of occluding and releasing lithium, but is preferably a lithium transition metal composite oxide Use things. Examples of such materials include lithium cobalt composite oxides such as LiCoO ₂ , lithium nickel composite oxides such as LiNiO ₂ , lithium manganese composite oxides such as LiMnO _{2, and the} like. In these lithium transition metal composite oxides, some of the main transition metal elements are Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si, etc. It can also be stabilized by replacing with other metal species, and is preferred.

  These positive electrode active materials may be used alone or in combinations of two or more in any combination.

  The method for producing a positive electrode using these positive electrode materials is not particularly limited. For example, it can be produced by adding a binder, a thickener, a conductive material, a solvent or the like to the above active material as necessary to form a slurry, applying the slurry to a substrate of a current collector, and drying. . Further, the active material can be roll-formed as it is to obtain a sheet electrode, or a pellet electrode by compression molding.

  The binder is not particularly limited as long as it is a material that is stable with respect to the solvent and electrolyte used in electrode production. Specific examples include polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, and isoprene rubber. And butadiene rubber.

  Examples of the thickener include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein.

  Examples of the conductive material include metal materials such as copper and nickel, and carbon materials such as graphite and carbon black. In particular, the positive electrode preferably contains a conductive material.

  The solvent used for the production of the positive electrode may be aqueous or organic. Examples of the aqueous solvent include water and alcohol, and examples of the organic solvent include N-methylpyrrolidone (NMP) and toluene.

  As the material for the current collector for the negative electrode, metals such as copper, nickel, and stainless steel are used, and among these, copper foil is preferable from the viewpoint of easy processing into a thin film and cost. The positive electrode current collector is made of a metal such as aluminum, titanium, or tantalum. Among these, aluminum foil is preferable from the viewpoint of easy processing into a thin film and cost.

  In the lithium ion secondary battery of the present invention, a separator is usually interposed between the positive electrode and the negative electrode in order to prevent a short circuit between the electrodes. The material and shape of the separator used in the lithium ion secondary battery of the present invention are not particularly limited, but it is preferable to select from materials that are stable with respect to the non-aqueous electrolyte solution of the present invention and have excellent liquid retention properties. It is preferable to use a porous sheet or nonwoven fabric made of polyolefin such as polyethylene and polypropylene.

  The lithium ion secondary battery of the present invention is manufactured by assembling the above-described nonaqueous electrolytic solution of the present invention, a positive electrode, a negative electrode, and a separator used as necessary into an appropriate shape. Furthermore, other components such as an outer case can be used as necessary. The method for assembling the battery is not particularly limited, and may be appropriately selected from methods usually employed.

  Also, the shape of the battery is not particularly limited, and a cylinder type in which a sheet electrode and a separator are spiraled, a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined, a coin type in which a pellet electrode and a separator are stacked, and the like are applied. Is possible.

  The use of the lithium ion secondary battery of the present invention is not particularly limited, and can be used for various known uses. Specific examples include notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, minidiscs, and transceivers. Electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting equipment, toys, game machines, watches, strobes, cameras, etc. In particular, since the lithium ion secondary battery of the present invention is excellent in cycle characteristics, excellent effects can be obtained in any of these applications.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist.

Example 1
[Production of negative electrode]
The d-value of the lattice plane (002) in X-ray diffraction is 0.336 nm, the crystallite size (Lc) is 652 nm, the ash content is 0.07% by weight, the median diameter by laser diffraction / scattering method is 12 μm, the BET specific surface area There 7.5 m ² / g, a peak PA (peak intensity IA) in the range of 1570～1620Cm ^-1 in the Raman spectrum analysis using an argon ion laser beam and scope of 1300～1400Cm ^-1 peak PB (peak intensity IB) intensity ratio R = IB / IA of the half width of the peak in the range of 0.12,1570～1620Cm ^-1 was used natural graphite powder is 19.9Cm ^-1 as the negative electrode active material. 94 parts by weight of this graphite powder was mixed with 6 parts by weight of polyvinylidene fluoride and dispersed with N-methyl-2-pyrrolidone to form a slurry. This was uniformly applied to one side of a 18 μm-thick copper foil as a negative electrode current collector, dried, and then pressed by a press machine so that the density of the negative electrode layer was 1.5 g / cm ³ to obtain a negative electrode.

[Production of positive electrode]
LiCoO ₂ was used as the positive electrode active material, and 6 parts by weight of carbon black and 9 parts by weight of polyvinylidene fluoride KF-1000 (trade name, manufactured by Kureha Chemical Co., Ltd.) were added to 85 parts by weight of this active material and mixed. The slurry dispersed with 2-pyrrolidone was uniformly applied to both surfaces of a 20 μm thick aluminum foil as a positive electrode current collector, and after drying, the density of the positive electrode layer was 3.0 g / cm by a press machine. Pressed to ³ to make a positive electrode.

[Preparation of electrolyte]
Under a dry argon atmosphere, LiPF ₆ sufficiently dried in a mixture of ethylene carbonate and ethyl methyl carbonate (volume ratio 3: 7) was dissolved to 1.0 mol / liter to obtain a blank electrolyte. Next, 1 part by weight of trimethylene glycol sulfite was added to 99 parts by weight of this blank electrolyte to prepare a desired electrolyte.

[Production of battery]
A battery element is manufactured by laminating the above positive electrode, negative electrode, and polyethylene separator in the order of the negative electrode, separator, positive electrode, separator, and negative electrode, and this battery element is a laminate in which both sides of bag-shaped aluminum are covered with a resin layer. After taking out the terminal of the positive electrode and the negative electrode in the film, the electrolytic solution was injected and vacuum-sealed to produce a sheet battery.

[Battery evaluation]
The sheet-like battery is sandwiched between glass plates in order to enhance the adhesion between the electrodes, and charged and discharged at a constant current corresponding to 0.2 C at 25 ° C. and a final charge voltage of 4.2 V and a final discharge voltage of 3 V. 3 is performed to stabilize the battery, and the fourth cycle is charged to a charge end voltage of 4.2 V with a current corresponding to 0.5 C, and charging is performed until the charge current value reaches a current value corresponding to 0.05 C. After 2V-constant current constant voltage charge (CCCV charge) (0.05C cut), 3V discharge was performed at a constant current value corresponding to 0.2C, and the discharge capacity before high temperature storage was measured. After 4.2V-CCCV (0.05C cut) charge was performed again, high temperature storage was performed under conditions of 85 ° C. and 72 hours. The battery after storage was discharged at a constant current of 0.2 C to a discharge starting voltage of 3 V at 25 ° C., and the remaining capacity was measured. Furthermore, 4.2V-CCCV (0.05C cut) charge is performed, and the recovery capacity (0.2C capacity) after high-temperature storage by discharging again to a discharge starting voltage of 3V with a constant current of 0.2C, then, The battery was charged under the same CCCV conditions, discharged to 3 V at a current value corresponding to 1 C, and each 1 C capacity was measured. Here, 1C represents a current value that can be fully charged in one hour.

  Table 1 shows the remaining capacity (%), recovery capacity (%), and 1C capacity (%) after high temperature storage when the discharge capacity before high temperature storage is 100.

(Example 2)
An electrolytic solution was prepared in the same manner as in Example 1 except that 1 part by weight of neopentyl glycol sulfite was added to 99 parts by weight of the blank electrolytic solution. A sheet-like battery was produced in the same manner as in Example 1 except that this electrolytic solution was used, evaluated in the same manner, and the results are shown in Table 1.

(Example 3)
An electrolytic solution was prepared in the same manner as in Example 1 except that 2 parts by weight of vinylene carbonate and 1 part by weight of trimethylene glycol sulfite were added to 97 parts by weight of the blank electrolytic solution. A sheet-like battery was produced in the same manner as in Example 1 except that this electrolytic solution was used, evaluated in the same manner, and the results are shown in Table 1.

Example 4
An electrolytic solution was prepared in the same manner as in Example 1 except that 2 parts by weight of vinylene carbonate and 1 part by weight of neopentyl glycol sulfite were added to 97 parts by weight of the blank electrolytic solution. A sheet-like battery was produced in the same manner as in Example 1 except that this electrolytic solution was used, evaluated in the same manner, and the results are shown in Table 1.

(Example 5)
An electrolytic solution was prepared in the same manner as in Example 1 except that 7 parts by weight of trimethylene glycol sulfite was added to 93 parts by weight of the blank electrolytic solution. A sheet-like battery was produced in the same manner as in Example 1 except that this electrolytic solution was used, evaluated in the same manner, and the results are shown in Table 1.

(Example 6)
An electrolytic solution was prepared in the same manner as in Example 1 except that 0.005 parts by weight of trimethylene glycol sulfite was added to 99.995 parts by weight of the blank electrolytic solution. A sheet-like battery was produced in the same manner as in Example 1 except that this electrolytic solution was used, evaluated in the same manner, and the results are shown in Table 1.

(Comparative Example 1)
An electrolytic solution was prepared in the same manner as in Example 1 except that the sulfite compound was not added and the blank electrolytic solution was used as the electrolytic solution. A sheet-like battery was produced in the same manner as in Example 1 except that this electrolytic solution was used, evaluated in the same manner, and the results are shown in Table 1.

(Comparative Example 2)
An electrolytic solution was prepared in the same manner as in Example 1 except that 2 parts by weight of vinylene carbonate was added to 98 parts by weight of the blank electrolytic solution and no sulfite compound was added. A sheet-like battery was produced in the same manner as in Example 1 except that this electrolytic solution was used, evaluated in the same manner, and the results are shown in Table 1.

  As is apparent from Table 1, when the non-aqueous electrolyte solution contains the sulfite compound represented by the general formula (I), the remaining capacity and the recovery capacity after high-temperature storage compared to Comparative Example 1 that does not contain the sulfite compound. It can also be seen that the 1C capacity is excellent. Moreover, when vinylene carbonate coexists as another negative electrode film forming agent, it turns out that it is excellent in a battery characteristic compared with the case where only vinylene carbonate is contained.

  According to the present invention, a high energy density lithium ion secondary battery having high charge / discharge efficiency and excellent storage characteristics and cycle characteristics even at high temperatures can be realized. It can utilize suitably in various fields, such as.

Claims (7)

In a non-aqueous electrolyte solution for a lithium ion secondary battery containing an electrolyte and a non-aqueous solvent, at least one sulfite compound represented by the following general formula (I) (provided that 4-isopropyl-5,5-dimethyl-1 is used) , 3,2-dioxathian-2-oxide and 5-methoxymethyl-5-methyl-1,3,2-dioxathian-2-oxide), and the content of the sulfite compound is non-aqueous A non-aqueous electrolyte for a lithium ion secondary battery, characterized by being 0.005 to 7% by weight based on the total weight of the electrolyte.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently one of the following:
Hydrogen atom, halogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclohexyl group, vinyl group, allyl group, and phenyl group ) The non-aqueous electrolyte solution for a lithium ion secondary battery according to claim 1, wherein the sulfite compound is any one of the following compounds.
(I) trimethylene glycol sulfite (ii) 5-fluoro-1,3,2-dioxathian-2-oxide (iv) 1,3-butanediol sulfite, 1,3-pentanediol sulfite, 2,4 -Pentanediol sulfite, neopentyl glycol sulfite, 4,4-dimethyl-1,3,2-dioxathian-2-oxide, 4-vinyl-1,3,2-dioxathian-2-oxide, 4-allyl- 1,3,2-dioxathian-2-oxide, 4-phenyl-1,3,2-dioxathian-2-oxide   3. The non-aqueous electrolyte for a lithium ion secondary battery according to claim 1, wherein the sulfite compound is at least one member selected from the group consisting of trimethylene glycol sulfite and neopentyl glycol sulfite. .   A negative electrode including a metal lithium, a lithium alloy, or a material capable of inserting and extracting lithium, a positive electrode including a material capable of inserting and extracting lithium, and a non-aqueous solvent in which a lithium salt is dissolved in a nonaqueous solvent A non-aqueous secondary battery comprising an aqueous electrolyte solution, wherein the non-aqueous electrolyte solution is the non-aqueous electrolyte solution according to any one of claims 1 to 3.   5. The lithium ion secondary battery according to claim 4, wherein the negative electrode contains a carbon material having a d-value of 0.335 to 0.34 nm on the lattice plane (002) plane in X-ray diffraction.   6. The lithium ion secondary battery according to claim 4, wherein the negative electrode contains an element selected from the group consisting of Si, Sn, Ge, and Al. In claims 4 to any one of 6, the negative electrode, the lithium ions comprising those selected from the group consisting of oxides and lithium alloy of a metal selected from Si and S n or Ranaru group Secondary battery.