JP2003157848A - Lithium ion nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithium ion nonaqueous electrolyte secondary battery having excellent high temperature resistance, capable of maintaining high stability when charging it and even under a high temperature. SOLUTION: This lithium ion nonaqueous electrolyte battery is provided with an positive electrode and a negative electrode using a material capable of doping and dedoping lithium ions as a positive electrode active material and a negative electrode active material, and a nonaqueous electrolyte obtained by dispersing an electrolyte in an nonaqueous medium. A sulfur compound is disposed at a position where it can be brought into contact with the nonaqueous medium. A sulfate compound is used as the sulfur compound. The specific area of the sulfate compound is 0.5-3.0 m<2> /g. The positive electrode and the negative electrode are formed by coating a positive electrode mix layer or a negative electrode mix layer on a strip collector. A rolled electrode formed by laminating/rolling the both electrodes through a separator is used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte secondary battery. More specifically, the present invention relates to a lithium ion non-aqueous electrolyte secondary battery in which high temperature stability is improved by arranging a sulfur compound in such a manner that it can come into contact with the non-aqueous electrolyte.

[0002]

2. Description of the Related Art In recent years, with the miniaturization and cordlessness of various electronic devices, there is an increasing demand for higher capacity and lighter weight of secondary batteries as a driving power source. Since a lithium secondary battery can have a higher capacity than a conventional secondary battery, various proposals have been made regarding a lithium ion non-aqueous electrolyte battery using doping / dedoping of lithium ions.

As a positive electrode active material for the above battery, LiCo
Lithium-transition metal composite oxides such as O ₂ and LiNiO ₂ are known, but when a battery using these positive electrode active materials is charged, decomposition and heat generation of the active material / electrolyte occur at high temperatures, There was a problem that the battery lacks stability when operated under the environment.

The following are possible causes of such decomposition. That is, it is known that when the positive electrode active material is charged and the lithium ions are extracted, the stability of the active material decreases and active oxygen is released when the active material is heated (for example, , Solid
State Physics, 69 , 265 (199)
4)), this active oxygen combines with the electrolytic solution to form an active peroxide intermediate, and decomposes the electrolytic solution in a chain reaction to reduce the stability of the battery at high temperatures.

On the other hand, in recent years, in order to ensure stability at high temperatures, a method of defining the average particle diameter of the active material and the like to reduce the contact area between the electrolytic solution and the active material (see, for example, Japanese Patent Laid-Open No. H9-90138).
No. 283144), a method of substituting a part of constituent elements of an active material with a different element (for example, JP-A-11-7958).
(Japanese Patent Laid-Open No. 8-37025), or a method using a flame-retardant non-aqueous electrolyte solution (for example, Japanese Patent Laid-Open No. 8-37025).
Conventionally, it has been used stably.

[0006]

However, in such a conventional method, since the properties of the active material itself must be changed, the original battery characteristics may be affected,
Further, there is a problem that the use is limited to an active material capable of substituting different elements. In addition, a higher degree of stability is required to realize a larger battery and a wider range of applications.

The present invention has been made in view of the above problems of the prior art, and is a lithium ion non-aqueous electrolyte secondary battery having excellent high temperature resistance, which maintains high stability during charging and under high temperature. The purpose is to provide a battery.

[0008]

As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by using a sulfur compound in a mode in which it can contact a non-aqueous electrolyte. The present invention has been completed.

That is, the lithium ion non-aqueous electrolyte secondary battery of the present invention comprises a positive electrode and a negative electrode each having a material capable of doping and dedoping lithium ions as a positive electrode active material or a negative electrode active material, and an electrolyte dispersed in a non-aqueous medium. In the lithium ion non-aqueous electrolyte secondary battery including the non-aqueous electrolyte formed as described above, a sulfur compound is arranged at a site that can come into contact with the non-aqueous medium.

[0010]

In the present invention, the sulfur compound is added and arranged at the site where it can come into contact with the non-aqueous electrolyte. Such a sulfur compound is used as an antioxidant that prevents deterioration of polymer materials and the like due to light and heat, and decomposes and stabilizes the peroxide intermediate. In the lithium ion non-aqueous electrolyte secondary battery of the present invention, the added sulfur compound is a non-aqueous electrolyte, specifically a non-aqueous medium in which the electrolyte is dispersed, specifically a non-aqueous solvent or gel form. Since it exists in the region where it can come into contact with the non-aqueous dispersion medium, it is thought to fulfill the function of decomposing and stabilizing the peroxide intermediate generated during charging and heating.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. As described above, in the lithium ion non-aqueous electrolyte secondary battery of the present invention, the sulfur compound is arranged at the site of the non-aqueous electrolyte that can come into contact with the non-aqueous medium, and this secondary battery is doped with lithium ions. In addition, it is provided with a non-aqueous electrolyte, and a positive electrode and a negative electrode whose positive electrode active material and negative electrode active material are materials that can be dedoped. In addition, in this specification, unless otherwise indicated, "%" shall show a mass percentage. Also, "non-aqueous electrolyte"
The term refers to an electrolyte in which the electrolyte is dispersed or dissolved in a non-aqueous medium, and in addition to the non-aqueous electrolytic solution in which the electrolyte is dissolved in a non-aqueous solvent such as propylene carbonate, the electrolyte is a gel-like non-aqueous dispersion medium (polyvinylidene fluoride). Polymers, etc.) are also included.

As the sulfur compound, any material can be used as long as it has a function of decomposing and / or stabilizing the peroxide intermediate as described above. Specifically, thiodipropion is used. Organic sulfur compounds such as acid esters and mercaptans, potassium sulfate, sulfates such as sodium sulfate and magnesium sulfate, sulfites and thiosulfates can be exemplified, but it is particularly preferable to use sulfates,
Among these, it is preferable to use an alkali metal or alkaline earth metal sulfate, for example, potassium sulfate or sodium sulfate. Regarding the above-mentioned sulfur compound,
You may use it in combination of 2 or more types as needed.

Further, the above-mentioned sulfur compound can be arranged in an appropriate state at a site which can contact the non-aqueous solvent or the non-aqueous dispersion medium constituting the non-aqueous electrolyte. It suffices if it is present at the site of contact, and specifically, in addition to being contained or attached to the positive electrode and / or the negative electrode, it may be contained or attached to a separator or the like in the vicinity thereof.

Here, the positive electrode and the negative electrode are typically a positive electrode mixture in which a positive electrode mixture containing an active material and a binder or a negative electrode mixture is coated on both surfaces of a current collector having a strip shape or a rectangular shape. A layer or a negative electrode mixture layer is formed. Therefore, when the positive electrode or the negative electrode contains the above-mentioned sulfur compound, it is usually sufficient to add the above-mentioned sulfur compound to the positive electrode mixture or the negative electrode mixture. When a sulfur compound is added to the positive electrode mixture or the negative electrode mixture, the addition amount thereof is preferably 0.3 to 15.0%, and more preferably 0.5 to 5% with respect to the weight of the mixture. More preferable.

The high temperature resistance in the case of adding the sulfur compound to the positive electrode mixture is due to the fact that the active intermediate generated due to the thermal decomposition of the positive electrode active material is stabilized by the sulfur compound. Conceivable. Therefore, it is desirable that the sulfur compound be uniformly dispersed in the positive electrode mixture or the negative electrode mixture. For that purpose, the specific surface area of the sulfur compound, specifically, the specific surface area by the BET method is 0.5 to 3.0 m ^2. /
It is preferable to adjust to g. If it is less than 0.5 m ² / g, the effect of addition may be exhibited but it may be insufficient. Also,
If it exceeds 3.0 m ² / g, the sulfur compound may absorb water and agglomerate, and the effect of addition may be insufficient.

The positive electrode active material in the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and known materials such as transition metal oxides capable of doping / dedoping lithium ions can be used. particularly preferred are the following general formulas _{~ Li x Ni 1-y M} y O 2-δ ... Li x Co 1-y M y O 2-δ ... Li x Mn 1-y M y O 2-δ ... _{li x Fe 1-y M y} O 2-δ ... ( the M in the formula Al, Fe, Cu, Co, Cr, Mg, C
a, V, Ni, Ag, Sn, B, Ga, Y, Zr, N
b, Mo, Tc, Ru, Rh, Pd and at least one element selected from the group consisting of Cd, x, y, z
And δ are 0 ≦ x ≦ 0.5, 0 ≦ y ≦ 1, and 0 ≦ z, respectively.
≦ 2, 0 ≦ δ ≦ 0.5) LiMn represented by
Lithium-containing oxides such as ₂ O ₄ and Li ₄ Mn ₅ O ₁₂ ;
Or the following general formula _{Li x Mn 2-y M y} O 4-δ ... (M in the formula indicates the and elements, x, y, respectively z and δ 0 ≦ x ≦ 1.5,0 ≦ y ≦ 1.5, 0 ≦ z ≦ 2,
Satisfying 0 ≦ δ ≦ 0.5). In the present invention, two or more of the above transition metal oxides can be used in combination.

On the other hand, as the negative electrode active material, metallic lithium and a carbonaceous material or an alloy material or a compound material capable of doping and dedoping lithium can be used, and it is also possible to use a combination of two or more thereof. Is. Of these negative electrode active materials, dope lithium
As the carbonaceous material that can be dedoped, for example, pyrolytic carbons, cokes, graphites, glassy carbons,
Examples include fired bodies of organic polymer compounds, carbon fibers, activated carbon, and polymers such as polyacetylene. Examples of the above cokes include pitch coke, needle coke, petroleum coke, and the like, and examples of the above organic polymer compound fired product include those obtained by carbonizing a phenol resin or a furan resin at an appropriate temperature.

Further, as the alloy material or the compound material, the following formula (1) M ^I _x M ^II _y Li _z (1) (wherein M ^I is a metal element capable of forming an alloy or compound with Li, M ^II represents a metal element other than Li and M ^I ,
x, y, and z each represent a number satisfying x> 0, y ≧ 0, and z ≧ 0). The metal element M ^I may be at least one element selected from the group consisting of 2A, 3B and 4B typical elements. On the other hand, the metal element M ^II
Include semiconductor elements such as B, Si and As, and specifically, Mg, B, Al, Ga, In, Si, Sn and P.
b, Sb, Bi, Cd, Ag, Zn, Hf, Zr and Y
Is included. Therefore, specific examples of the compound represented by the above formula (1), Li-Al alloy, ^{Li-Al-M I}
Alloys (M ^I represents at least one element selected from the group consisting of 2A, 3B and 4B group typical elements), AlS
b, CuMgSb, etc. can be mentioned.

Further, the above metal element M^IAs a 4B family
It is preferable to use a typical element, preferably Si or S
n, and Si is more desirable. From this point of view,
As the compound represented by the formula (1), M^II _ySi or M
^II _ySn (M^IIIndicates a metal element other than Si or Sn
The compound represented by
_Four, SiB₆, Mg_TwoSi, Mg_TwoSn, Ni_TwoSi,
TiSi_Two, MoSi_Two, CoSi_Two, NiSi_Two, C
aSi_Two, CrSi_Two, Cu₅Si, FeSi_Two, Mn
Si_Two, NbSi_Two, TaSi_Two, VSi _Two, WSi_Two
And ZnSi_TwoAnd so on.

Further, it may contain one or more kinds of non-metal elements and metal elements other than the typical 4B group excluding carbon element. In this case, as the compound represented by the above formula (1), SiC, Si ₃ N ₄ , Si ₂ N ₂ O, Ge ₂ N
₂ O, SiO _x (0 <x ≦ 2), SnO _x (0 <x ≦
2), LiSiO and LiSnO may be mentioned.

The above-mentioned carbonaceous material or alloy material may be doped with lithium electrochemically in the battery after the battery is manufactured, or after the battery is manufactured or before the battery is manufactured.
It may be electrochemically doped by being supplied from a positive electrode or a lithium source other than the positive electrode. Alternatively, the material may be synthesized as a lithium-containing material during material synthesis, and may be contained in the negative electrode active material during battery production.

In the non-aqueous electrolyte secondary battery of the present invention, the positive electrode or the negative electrode is, as described above, a positive electrode mixture containing the above active materials and a binder on both surfaces of the current collector having a strip shape or a rectangular shape. It is produced by forming a positive electrode mixture layer or a negative electrode mixture layer coated with an agent or a negative electrode mixture. Here, the current collector is not particularly limited as long as it has a current collecting function, but an aluminum foil is preferably used for forming the positive electrode, and a copper foil or a nickel foil that does not form an alloy with lithium is preferably used for forming the negative electrode. be able to. Further, the positive electrode mixture or the negative electrode mixture can be obtained by mixing a known binder such as polyvinylpyrrolidone or the like and a known additive such as a conductive agent such as graphite, if necessary, in addition to the above active material. The formation of the positive electrode mixture layer or the negative electrode mixture layer is typically performed by applying the positive electrode mixture or the negative electrode mixture on both surfaces of the current collector and drying.

Further, in the present invention, the positive electrode, the negative electrode, and the separator as described above are typically formed in a strip shape or a rectangular shape in order to increase the capacity, and the positive electrode sheet and the negative electrode are formed. A laminated sheet is formed by inserting a separator between the laminated sheet and the sheet, and a wound electrode is formed by winding the laminated sheet to form a battery.
The mode of winding is not particularly limited, and it may be spiral or spiral, and is usually wound many times to produce a wound electrode.

It is sufficient for the separator to have a function of separating the positive electrode and the negative electrode and preventing a short circuit due to physical contact between them, but specifically, a film made of microporous polyethylene or polypropylene. It is preferable to use, and since such a microporous film is softened at a high temperature to close the micropores and suppress the outflow of lithium ions, it can be suitably used as a measure against overcurrent. From the relationship between lithium ion conductivity and energy density, the thickness of the separator is preferably as thin as possible, typically 50 μm or less.

In the lithium ion non-aqueous electrolyte secondary battery of the present invention, the non-aqueous electrolyte means the one as described above, but the non-aqueous electrolytic solution in which the electrolyte is dissolved in the non-aqueous solvent and the gel-like electrolyte are used. It can be roughly classified into a gel electrolyte dissolved in a non-aqueous dispersion medium. Here, as the electrolyte to be dissolved in the non-aqueous solvent or dispersed in the gel non-aqueous dispersion medium, for example, Li
Cl, LiBr, LiClO ₄ , LiAsF ₆ , LiP
_{F 6, LiBF 4, LiCH 3} SO 3, LiCF 3 SO
₃ , Li (CF ₃ SO ₂ ) ₂ or LiB (C ₆ H ₅ ) ₄
And mixtures thereof can be used, and among these, it is particularly preferable to use LiPF ₆ or LiBF ₄ .

As the non-aqueous solvent, an aprotic solvent such as propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, γ-butyl lactone, sulfolane, methyl sulfolane, 1 is used as in the conventional non-aqueous lithium battery. , 2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, methyl propionate, methyl butyrate, dimethyl carbonate, propionitrile , Anisole, acetate, butyrate, propionate and the like.
In particular, from the viewpoint of voltage stability, it is preferable to use cyclic carbonates such as propylene carbonate and vinylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate and dipropyl carbonate. Moreover, such non-aqueous solvents may be used alone or in combination of two or more.

On the other hand, as the gel-like non-aqueous dispersion medium,
Mention may be made of polymers such as polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate, polyethylene oxide and polysiloxane. The molecular weight of these polymers is preferably about 300,000 to 800,000. The dispersion of the electrolyte in the polymer is typically
It can be performed by dissolving a polymer such as polyvinylidene fluoride in a non-aqueous electrolytic solution in which an electrolyte is dissolved in a non-aqueous solvent and forming a sol.

As described above, the lithium ion non-aqueous electrolyte secondary battery of the present invention has the non-aqueous electrolyte, the positive electrode, the negative electrode, and the sulfur compound as essential constituents, but the battery shape is not particularly limited. Instead, for example, various battery shapes such as a cylindrical shape, a square shape, a coin shape, and a button shape can be adopted.

[0029]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples.

(Example 1) First, a lithium-cobalt composite oxide as a positive electrode active material was prepared as follows.
A mixture of 2 mol of cobalt oxide and 3 mol of lithium carbonate was calcined in air at a temperature of 900 ° C. for 5 hours to obtain LiCo.
O ₂ was produced. Next, commercially available crystals of potassium sulfate were crushed using a vibration mill to obtain powder having a specific surface area of 1.0 m ² / g. The specific surface area is measured by the BET method (BET one-point method).

The LiCoO ₂ prepared as described above was 85%, potassium sulfate was 1%, graphite was 10% as a conductive agent, and polyvinylidene fluoride (PV) was a binder.
DF) 4% and mixed with N-methyl-2-pyrrolidone (N
MP) to obtain a positive electrode mixture slurry. This slurry was uniformly applied to a strip-shaped aluminum foil having a thickness of 20 μm, dried, and then compressed with a roller press machine and punched into a predetermined size to obtain a positive electrode. The packing density of this positive electrode was measured and found to be 3.4 g / cm ³ .

Next, in order to produce a negative electrode, 90% of powdered artificial graphite was mixed with 10% of PVDF and dispersed in NMP to obtain a negative electrode mixture slurry. This negative electrode mixture slurry was uniformly applied to a copper foil having a thickness of 10 μm, dried, compressed with a roller press machine, and punched into a predetermined size to obtain a negative electrode.

The positive electrode and the negative electrode produced as described above were laminated via a known porous polyolefin film to produce a coin cell of this example having a diameter of 20 mm and a height of 1.6 mm. Here, as the electrolytic solution, non-aqueous electrolysis prepared by dissolving LiPF ₆ in a mixed solution of ethylene carbonate and methyl ethyl carbonate at a volume mixing ratio of 1: 1 so as to have a concentration of 1 mol / dm ^3. The liquid was used.

(Examples 2 to 4) The specific surface area of potassium sulfate was changed to 0.5 (Example 2), 1.5 (Example 3) and 3.0 (Example 4) m ² / g, respectively. Example 1
The same operation was repeated to prepare the coin cell of each example.

(Comparative Examples 1 and 2) The specific surface area of potassium sulfate was 0.1 (Comparative Example 1) and 3.5 (Comparative Example 2) m ² /
The same operation as in Example 1 was repeated except that g was changed to produce coin cells of each example.

(Examples 5 to 16) The same operation as in Examples 1 to 4 was repeated except that sodium sulfate, magnesium sulfate and sodium thiosulfate were used in place of potassium sulfate, to produce coin cells of each example.

Comparative Examples 3 to 8 Coin cells of each example were prepared by repeating the same operations as in Comparative Examples 1 and 2, except that sodium sulfate, magnesium sulfate and sodium thiosulfate were used instead of potassium sulfate.

Regarding the coin cells of the respective examples produced as described above, first, the charging voltage was 4.20 V and the charging current was 1 m.
A, the charging time was 15 hours. Next, the positive electrode mixture was taken out, and this was used as a sample together with an electrolytic solution for differential scanning calorimetry (DSC) to determine the heat generation amount and the heat generation start temperature during heating. The apparatus used is DSC220U (trade name) manufactured by Seiko Instruments Inc. Table 1 shows the relationship between the specific surface area of the sulfur compound and the discharge capacity, the calorific value, and the exothermic start temperature obtained from the test using the coin cells manufactured in the above-mentioned Examples and Comparative Examples.

[0039]

[Table 1]

From Table 1, the specific surface area of the inorganic salt is 0.5 to
In the case of 3.0, the amount of heat generation can be effectively suppressed, and the heat generation start time also changes to the high temperature side. That is, it can be said that the stability of the electrode at high temperature is improved.

Example 17 A coin cell of this example was produced by repeating the same operation as in Example 1 except that potassium sulfate was added to the negative electrode mixture instead of adding potassium sulfate to the positive electrode.

(Examples 18 to 20) The same as Example 1 except that the specific surface area of potassium sulfate was 0.5, 1.5 and 3.0 m ² / g and potassium sulfate was added to the negative electrode mixture. The operation was repeated to produce the coin cell of each example.

Comparative Examples 9 and 10 Example 1 was repeated except that the specific surface area of potassium sulfate was changed to 0.1 and 3.5 m ² / g.
The same operation as in 7 was repeated to produce the coin cell of each example.

(Examples 21 to 32) The coin cell of each example was produced by repeating the same operation as in Example 17 except that sodium sulfate, magnesium sulfate and sodium thiosulfate were used instead of potassium sulfate.

(Comparative Examples 11 to 16) The same operation as in Comparative Examples 1 and 2 was repeated except that sodium sulfate, magnesium sulfate and sodium thiosulfate were used in place of potassium sulfate, to produce coin cells of each example.

Table 2 shows the relationship between the specific surface area of potassium sulfate, the discharge capacity, the calorific value, and the exothermic start temperature, which were obtained from the results of thermal analysis of the above batteries.

[0047]

[Table 2]

From Table 2, it can be seen that the same as in the case of adding to the positive electrode.
Specific surface area of machine salt is 0.5-3.0m ^TwoEffective when / g
The heat generation amount can be suppressed, and the heat generation start temperature is also on the high temperature side.
Is changing.

(Examples 33 and 34) Instead of adding 1% of potassium sulfate to the positive electrode, potassium sulfate of 5% (L
iCoO ₂ is 81%, 10% (LiCoO ₂ is 76%)
%) The coin cell of each example was produced by repeating the same operation as in Example 1 except that the addition was performed.

(Examples 35 to 40) Except that the specific surface area of potassium sulfate was 0.5, 1.5 and 3.0 m ² / g,
The same operation as in Examples 33 and 34 was repeated to produce coin cells of each example.

Comparative Examples 17 to 20 Example ² was repeated except that the specific surface area of potassium sulfate was changed to 0.1 and 3.5 m ² / g.
The same operation as 5 and 26 was repeated to manufacture coin cells of each example.

Table 3 shows the relationship between the specific surface area of potassium sulfate and the discharge capacity, the calorific value, and the exothermic start temperature, which were obtained from the results of thermal analysis of the above batteries.

[0053]

[Table 3]

From Table 3, the specific surface area of the inorganic salt is 0.5 to
In the case of 3.0 m ² / g, the amount of heat generation can be effectively suppressed, and the heat generation start temperature also changes to the high temperature side. As described above, in the above examples, when a compound containing sulfur is added to a non-aqueous electrolyte secondary battery, which is an example of a non-aqueous electrolyte secondary battery, the specific surface area thereof is 0.5 to 3.0 m ² / By setting to g, these compounds are uniformly dispersed in the positive electrode mixture or the negative electrode mixture, and the effect is satisfactorily exhibited. In this respect, it can be said that the above examples show suitable conditions for adding the sulfur compound in the lithium ion non-aqueous electrolyte secondary battery. At this point, from the viewpoint of the discharge capacity, the heat generation amount, and the heat generation start temperature, Examples 1, 3
And 4 can be said to be the most suitable examples.

Although the present invention has been described in detail with reference to the preferred embodiments, the present invention is not limited to these embodiments, and various modifications can be made without departing from the gist of the present invention. For example, the present invention discloses to suppress the formation of a peroxide intermediate due to active oxygen that may occur from an active material, and a material having such a function is a sulfur compound or It is believed that it can be used instead of the sulfate compound.

[0056]

As described above, according to the present invention, since the sulfur compound is used in such a manner that it can come into contact with the non-aqueous electrolyte, it maintains high stability during charging and under high temperature, and has high temperature resistance. An excellent lithium ion non-aqueous electrolyte secondary battery can be provided.

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Claims (6)

[Claims] 1. A lithium-ion non-aqueous electrolyte comprising a positive electrode and a negative electrode, wherein a material capable of doping and de-doping lithium ion is used as a positive electrode active material or a negative electrode active material, and a non-aqueous electrolyte formed by dispersing an electrolyte in a non-aqueous medium. In the secondary battery, a lithium ion non-aqueous electrolyte secondary battery in which a sulfur compound is arranged at a site that can come into contact with the non-aqueous medium. 2. The lithium ion non-aqueous electrolyte secondary battery according to claim 1, wherein the sulfur compound is a sulfuric acid compound and has a specific surface area of 0.5 to 3.0 m ² / g. 3. The lithium ion non-aqueous electrolyte secondary battery according to claim 2, wherein the sulfuric acid compound is an alkali metal sulfuric acid compound or an alkaline earth metal sulfuric acid compound. 4. The lithium ion non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material is a composite compound of lithium and a transition metal. 5. The lithium-ion non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode active material is a carbonaceous material or a material that can be alloyed or combined with lithium. 6. The positive electrode and the negative electrode are formed by coating a belt-shaped current collector with a positive electrode mixture layer or a negative electrode mixture layer containing the positive electrode active material or the negative electrode active material, with both electrodes interposed by a separator. The lithium ion non-aqueous electrolyte secondary battery according to claim 1, further comprising a wound electrode formed by stacking and winding.