JP2001185213A - Nonaqueous electrolyte battery and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte battery, having superior properties for high charge-discharge rate and for low-temperature charge-discharge. SOLUTION: In the nonaqueous electrolyte battery, compounds in which at least one halogen group or the other substituent group except for halogen is bonded to the benzene ring, in which the bonded atom of substituent group, except for halogen, is one kind selected from among the groups consisting of carbon, nitrogen, or sulfur are contained in the electrolyte.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous electrolyte battery and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, electronic devices such as a portable radio telephone, a portable personal computer, and a portable video camera have been developed, and various electronic devices have been reduced in size to be portable. Along with this, a battery having a high energy density and a light weight is also adopted as a built-in battery. A typical battery that satisfies such a requirement is an active material such as lithium metal or lithium alloy, or a host material containing lithium ions (here, a host material refers to a material that can occlude and release lithium ions). Lithium intercalation compound occluded in a certain carbon is used as a negative electrode material, and LiC
This is a non-aqueous electrolyte secondary battery using an aprotic organic solvent in which a lithium salt such as 10 ₄ or LiPF ₆ is dissolved as an electrolyte.

This non-aqueous electrolyte secondary battery has a negative electrode plate in which the above-mentioned negative electrode material is held on a negative electrode current collector as a support, and a reversible electrochemical reaction with lithium ions such as a lithium-cobalt composite oxide. The positive electrode plate, which holds the positive electrode active material that reacts on the positive electrode current collector that is the support, from the separator that holds the electrolytic solution and intervenes between the negative electrode plate and the positive electrode plate to prevent a short circuit between the two electrodes Has become.

[0004] Each of the positive electrode plate and the negative electrode plate is formed into a thin sheet or foil shape, and is a power generating element formed by sequentially laminating or spirally winding through a separator. The power generation element is housed in a battery container made of a metal can made of stainless steel, nickel-plated iron, or aluminum, or a battery container made of a material obtained by laminating a metal foil with a resin film, and injecting an electrolytic solution. rear,
The battery case is sealed and the battery is assembled.

When such a non-aqueous electrolyte secondary battery is used in electronic equipment, a predetermined voltage is obtained as a unit cell or a plurality of cells connected in series. The single or plural batteries are housed in a housing made of resin or metal and resin together with the charge / discharge control circuit, and sealed so that the contents cannot be taken out, and used as a battery pack.

In order to improve the overcharge safety of a battery, 4-bromo-1,2-dimethoxybenzene,
It has been proposed to add 4-fluoro-1,2-dimethoxybenzene and the like to the electrolyte (J. Elec).
trochem. Soc. , 146 , 1256 (19
99)). This report proposes that when the battery is overcharged, the additive promotes self-discharge by moving back and forth between the positive electrode and the negative electrode as a redox agent, thereby suppressing the progress of overcharge. I have.

[0007]

However, in a non-aqueous electrolyte, since the transport number of cations involved in the electrode reaction is usually 0.5 or less, the charge / discharge characteristics are governed by the ion concentration diffusion. Moreover, since the non-aqueous electrolyte has a higher viscosity than the aqueous electrolyte, the ion diffusion coefficient is small. Therefore, the non-aqueous electrolyte battery has a problem that the high-rate charge / discharge characteristics are inferior to batteries using an aqueous electrolyte such as a nickel-cadmium battery and a nickel-hydrogen battery. In particular, at low temperatures, the viscosity of the non-aqueous electrolyte increases and the ionic diffusion coefficient decreases, so that there has been a problem that the high-rate charge / discharge characteristics are significantly poor.

Therefore, a non-aqueous electrolyte battery excellent in high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics has been demanded.

[0009]

The non-aqueous electrolyte battery according to the present invention has been made in view of the above problems, and has at least one halogen and a substituent other than a halogen bonded to a benzene ring. A compound in which the atom bonded to the benzene ring of the other substituent is one selected from the group consisting of carbon, nitrogen and sulfur (hereinafter, this compound is abbreviated as "halogen-bonded benzene compound") in the electrolyte solution It is characterized by.

Further, in the present invention, the substituent other than the halogen is one selected from the group consisting of an alkyl group, a cyano group, a nitro group, an amino group, a sulfone group, a carbonyl group, a carboxyl group and an aldehyde group. It is characterized by.

The present invention is also characterized in that, in the above nonaqueous electrolyte battery, the halogen is fluorine and the halogen-bonded benzene compound is fluorobenzene.

Further, the present invention is characterized in that, in the above nonaqueous electrolyte battery, the concentration of the compound having a halogen bonded to a benzene ring in the electrolytic solution is 0.01 wt% or more and 15 wt% or less.

In the present invention, the primary particles have a particle diameter of 0.5.
A positive electrode active material having a size of not less than μm and not more than 30 μm or a negative electrode active material having a primary particle size of not less than 3 μm and not more than 50 μm is provided.

Further, the method for producing a non-aqueous electrolyte battery according to the present invention is a method for producing a non-aqueous electrolyte battery provided with a negative electrode having carbon, wherein a compound having a halogen bonded to a benzene ring is added after a charging step. It is characterized in that it is added into the battery.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS By adding a halogen-bonded benzene compound to an electrolytic solution, a non-aqueous electrolyte battery having excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics can be obtained.

In the halogen-bonded benzene compound, the substituent other than halogen is one selected from an alkyl group, a cyano group, a nitro group, an amino group, a sulfone group, a carbonyl group, a carboxyl group and an aldehyde group. In this case, a nonaqueous electrolyte battery having excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics can be obtained.

In the present invention, when a compound in which the halogen-bonded benzene compound is fluorine is added to the electrolytic solution, particularly excellent high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics can be obtained. In this case, more excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics can be obtained.

According to the present invention, the concentration of the halogen-bonded benzene compound in the electrolytic solution is from 0.01 wt% to 15 wt%.
%, It was confirmed by experiments described later that particularly excellent high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics were obtained.

The present invention is particularly effective when the non-aqueous electrolyte contains at least one of diethyl carbonate and methyl ethyl carbonate. When diethyl carbonate or methyl ethyl carbonate is used in the non-aqueous electrolyte, the electrolytic solution is less likely to be oxidized and decomposed when left at a high temperature in a charged state than in the case where dimethyl carbonate is used, and the battery case due to an increase in the pressure inside the battery. An excellent battery with small swelling can be obtained.

However, since diethyl carbonate and methyl ethyl carbonate have a higher viscosity than dimethyl carbonate, diffusion of ions in the electrolyte is slowed, and high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics are low. There was a problem that it decreased. Therefore, it has been extremely difficult to manufacture a battery having excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics and having a small battery case swelling when left in a charged state at a high temperature.

In the case of using the present invention, by using at least one of diethyl carbonate and methyl ethyl carbonate in the non-aqueous electrolyte and using an electrolytic solution containing a halogen-bonded benzene compound,
It is possible to manufacture a battery that has excellent high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics, and that has a small swelling of the battery case when left at high temperature in a charged state.

The present invention is particularly effective when the positive electrode active material contains a lithium nickel composite oxide or a lithium manganese composite oxide. The lithium nickel composite oxide and the lithium manganese composite oxide are less expensive than the lithium cobalt composite oxide. However, when the lithium nickel composite oxide or lithium manganese composite oxide is used as the positive electrode active material, the charge / discharge characteristics at a high rate and the low-temperature charge / discharge characteristics are lower than when the lithium cobalt composite oxide is used. There was a problem that it was inferior. Therefore, it has been very difficult to manufacture a low-cost battery that is excellent in high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics.

In the case of using the present invention, high-rate charge / discharge characteristics can be obtained by using an electrolyte containing a lithium nickel composite oxide or a lithium manganese composite oxide as well as a halogen-bonded benzene compound. In addition, it is possible to manufacture a battery which is excellent in charge / discharge characteristics at low temperature and inexpensive.

The present invention is particularly effective in a non-aqueous electrolyte battery provided with a polymer electrolyte in contact with at least one of the positive electrode active material and the negative electrode active material. By using the polymer electrolyte in contact with the active material, the amount of the organic electrolyte in contact with the active material can be reduced, and the amount of gas generated by the reaction between the active material and the electrolyte when left at a high temperature can be reduced. . As a result, the problem that the battery swells when left at high temperature can be solved.

However, in the polymer electrolyte, there is a problem that high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics are inferior due to slow diffusion of ions. Therefore, it has been extremely difficult to produce a battery that has excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics and that does not easily swell when left at high temperatures. When the present invention is used, the polymer electrolyte is provided, and by using an electrolyte solution containing a halogen-bonded benzene compound, the high-rate charge / discharge characteristics and the charge / discharge characteristics at a low temperature are excellent. It is possible to manufacture a battery that does not easily swell.

The present invention is particularly effective in a non-aqueous electrolyte battery having carbon in the negative electrode and at least one of the positive electrode and the negative electrode having a thickness of 120 μm or more. By increasing the thickness of at least one of the positive electrode or the negative electrode,
The ratio of the error of the active material layer thickness to the active material layer thickness can be reduced. Therefore, a uniform positive / negative capacity ratio is maintained at any part of the positive / negative electrode, the deposition of metallic lithium on the negative electrode can be suppressed, and a decrease in the cycle life of the battery can be suppressed.

However, when the thickness of the positive electrode or the negative electrode is increased, the distance over which ions must move in the electrolyte becomes longer, and thus the high-rate charge-discharge characteristics and the charge-discharge characteristics at low temperatures are inferior. there were. Therefore,
In order to obtain a non-aqueous electrolyte battery having excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics, the thickness of the positive and negative electrodes must be
It was necessary to be less than 20 μm. For these reasons, it has been very difficult to produce a battery that has excellent high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics, as well as excellent cycle life.

When the present invention is used, the thickness is 120 μm.
m or more, by using an electrolyte solution containing a halogen-bonded benzene compound together,
A battery having excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics, as well as excellent cycle life characteristics, can be manufactured.

The present invention is particularly effective in a non-aqueous electrolyte battery provided with a short-circuit prevention film between the positive electrode and the negative electrode, wherein the porosity of the short-circuit prevention film is 65% or less. By lowering the porosity of the short-circuit preventing film, the mechanical strength of the short-circuit preventing film is increased, so that an internal short circuit is less likely to occur during battery production. However, when the porosity of the short-circuit prevention film is reduced,
Since the ion transmission path between the positive electrode and the negative electrode is narrowed, there is a problem that the high-rate charge / discharge characteristics and the charge / discharge characteristics at a low temperature are inferior.

Therefore, in order to obtain a non-aqueous electrolyte battery having excellent high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics,
The porosity of the short circuit prevention film had to be higher than 65%. For these reasons, it has been very difficult to manufacture a battery that has excellent high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics and is less likely to cause internal short circuits.

When the present invention is used, in addition to the fact that the porosity of the short-circuit preventing film is 65% or less and the use of an electrolytic solution containing a halogen-bonded benzene compound, high-rate charge / discharge characteristics and low temperature It is possible to manufacture a battery which is excellent in charge-discharge characteristics at the same time and hardly causes an internal short circuit.

The present invention is particularly effective in a non-aqueous electrolyte battery provided with a short-circuit prevention film between the positive electrode and the negative electrode, wherein the short-circuit prevention film has an average pore size of 3 μm or less. By reducing the hole diameter of the short-circuit prevention film, the dropped active material particles are less likely to enter the holes, and an internal short circuit is less likely to occur during battery manufacture. However, when the pore diameter of the short-circuit prevention film is reduced, ions are difficult to diffuse between the positive electrode and the negative electrode, and there is a problem that high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics are inferior.

Therefore, in order to obtain a nonaqueous electrolyte battery having excellent high rate charge / discharge characteristics and low temperature charge / discharge characteristics,
It was necessary to make the average pore diameter of the short circuit prevention film larger than 3 μm. For these reasons, it has been very difficult to manufacture a battery that has excellent high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics and is less likely to cause internal short circuits.

When the present invention is used, in addition to the fact that the average pore size of the short-circuit preventing film is 3 μm or less and the use of an electrolytic solution containing a halogen-bonded benzene compound, high-rate charge / discharge characteristics and low-temperature It is possible to manufacture a battery that has excellent charge / discharge characteristics and hardly causes an internal short circuit.

According to the present invention, the primary particles have a particle diameter of 0.5 μm.
The particle diameter of the positive electrode active material or the primary particles is 3 μm
It is particularly effective in a non-aqueous electrolyte battery provided with the negative electrode active material described above. By increasing the size of the active material particles, the surface area of the active material is reduced, and the amount of gas generated by the reaction between the active material and the electrolyte when left at a high temperature can be reduced. As a result, the problem that the battery swells when left at high temperature can be solved.

However, when the size of the active material particles is increased, a rapid electrode reaction becomes difficult to occur due to a decrease in the electrode surface area, and there is a problem that high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics are inferior. . Therefore, in order to obtain a nonaqueous electrolyte battery having excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics, the particle diameter of the primary particles of the positive electrode active material is smaller than 0.5 μm, The particle size had to be smaller than 3 μm. For these reasons, it has been very difficult to manufacture a battery that has excellent high-rate charge-discharge characteristics and low-temperature charge-discharge characteristics, and that does not easily swell when left at high temperatures.

In the case of using the present invention, in addition to providing a positive electrode active material having primary particles having a particle diameter of 0.5 μm or more or a negative electrode active material having primary particles having a particle diameter of 3 μm or more, a halogen bond By using an electrolytic solution containing a benzene compound, it is possible to manufacture a battery that is excellent in high-rate charge / discharge characteristics and charge / discharge characteristics at low temperatures and that does not easily swell when left at high temperatures.

In a nonaqueous electrolyte battery provided with carbon in the negative electrode, a film is formed on the carbon surface at the time of the first charge, so that subsequent decomposition of the electrolytic solution at the negative electrode is suppressed. However, when a halogen-bonded benzene compound is added to the electrolytic solution, the ion permeability of the film formed on the surface of the carbon negative electrode slightly decreases.

Therefore, by performing a charging step using an electrolyte solution containing no halogen-bonded benzene compound, a film having high ion permeability is formed on the carbon surface, and then the halogen-bonded benzene compound is added into the battery. In addition, it is possible to suppress a decrease in ion permeability of the film. As a result, a non-aqueous electrolyte having particularly excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics can be manufactured by this manufacturing method.

The power generating element according to the present invention may be either a positive electrode plate or a negative electrode plate formed into a thin sheet or foil shape, which are sequentially laminated or spirally wound. .

The material of the battery case may be any of a sheet in which a metal foil and a resin film are bonded, iron, or aluminum.

When a sheet in which a metal foil and a resin film are bonded to each other is used as the material of the battery case, aluminum, an aluminum alloy, titanium foil, or the like should be used as the metal material of the metal laminated resin film. Can be. As the material of the heat-welded portion of the metal laminate resin film, any material may be used as long as it is a thermoplastic polymer material such as polyethylene, polypropylene, and polyethylene terephthalate.

Further, the resin layer and the metal foil layer of the metal laminated resin film are not limited to one layer each, but may be two or more layers. As the cell case, a laminated case formed into an envelope shape by heat welding a metal laminated resin film, a case in which four sides of two metal laminated resin sheets are heat welded, or one sheet folded in two A metal-laminated resin film case of any shape can be used, such as a case in which the three sides are heat-welded and a metal-laminated resin sheet formed by press-forming a metal-laminated resin sheet into a cup-like shape and a power generation element.

The electrolyte solvent used in the nonaqueous electrolyte battery according to the present invention includes ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, sulfolane, dimethyl sulfoxide, acetonitrile, dimethylformamide,
Dimethylacetamide, 1,2-dimethoxyethane,
1,2-diethoxyethane, tetrahydrofuran, 2-
A polar solvent such as methyl tetrahydrofuran, dioxolan, methyl acetate, or a mixture thereof may be used.

The lithium salts dissolved in the organic solvent include LiPF ₆ , LiClO ₄ , LiBF ₄ , LiAs
F ₆ , LiCF ₃ CO ₂ , LiCF ₃ SO ₃ , LiN (SO ₂
CF ₃ ) ₂ , LiN (SO ₂ CF ₂ CF ₃ ) ₂ , LiN (CO
Salts such as CF ₃ ) ₂ and LiN (COCF ₂ CF ₃ ) ₂ or mixtures thereof may be used.

The short-circuit preventing film of the non-aqueous electrolyte battery according to the present invention may be a material obtained by impregnating an electrolytic solution into an insulating microporous polyethylene film, a solid polymer electrolyte, or a solid polymer electrolyte containing an electrolytic solution. A gelled electrolyte or the like can also be used. Further, an insulating microporous film and a solid polymer electrolyte may be used in combination. Further, when a porous solid polymer electrolyte membrane is used as the solid polymer electrolyte, the electrolyte contained in the polymer and the electrolyte contained in the pores may be different.

Further, as a compound capable of inserting and extracting lithium as a cathode material, an inorganic compound is represented by a composition formula L
i _x MO ₂ or Li _y M ₂ O _4, (where M is a transition metal,
A composite oxide represented by 0 ≦ x ≦ 1, 0 ≦ y ≦ 2),
An oxide having tunnel-like holes and a metal chalcogenide having a layered structure can be used. As specific examples, LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , Li
₂ Mn ₂ O ₄ , MnO ₂ , FeO ₂ , V ₂ O ₅ , V ₆ O ₁₃ , T
iO ₂ , TiS _{2 and the} like. Examples of the organic compound include a conductive polymer such as polyaniline. Further, the above-mentioned various active materials may be mixed and used regardless of an inorganic compound or an organic compound.

Further, as a compound as a negative electrode material, A
Alloys of lithium with l, Si, Pb, Sn, Zn, Cd, etc., tin oxides, transition metal oxides such as LiFe ₂ O ₃ , WO ₂ , MoO ₂ , carbonaceous materials such as graphite, carbon, Li ₅ Lithium nitride such as (Li ₃ N) or metallic lithium foil, or a mixture thereof may be used.

The present invention is not limited to a secondary battery, but may be applied to a primary battery using lithium metal as a negative electrode active material and manganese oxide, carbon fluoride or thionyl chloride as a positive electrode active material. Good.

[0050]

Next, the present invention will be described based on preferred embodiments.

Example 1 A lithium-cobalt composite oxide having an average primary particle size of 0.5 μm was used as a positive electrode active material. The positive electrode plate is obtained by holding the above-mentioned lithium cobalt composite oxide as an active material on a current collector. An aluminum foil having a thickness of 20 μm was used for the current collector. The positive electrode plate was prepared by mixing 6 parts of polyvinylidene fluoride as a binder and 3 parts of acetylene black as a conductive agent together with 91 parts of an active material, appropriately adding N-methylpyrrolidone to prepare a paste, and then collecting the paste. It was manufactured by applying on both sides of an electric conductor material, drying and pressing. The thickness of one side of the active material layer of the positive electrode plate was 60 μm, and the thickness of the positive electrode plate together with the current collector was 120 μm.

The negative electrode plate has graphite (average primary particle size: 3 μm) 92 as a host material on both surfaces of the current collector.
The mixture was mixed with 8 parts of polyvinylidene fluoride as a binder, N-methylpyrrolidone was appropriately added to prepare a paste, applied, dried, and pressed. A 14-μm-thick copper foil was used as the current collector of the negative electrode plate. The thickness of one side of the active material layer of the negative electrode plate was 63 μm, and the thickness of the negative electrode plate together with the current collector was 120 μm.

The short-circuit prevention film has a porosity of 65% and an average pore diameter of 3 μm.
m of polyethylene microporous membrane. The dimensions of the electrode plate are 49 mm in width for the positive electrode plate, 25 μm in thickness for the separator, and 53 m in width.
m, the negative electrode plate has a width of 51 mm, and the lead terminals are welded to the positive electrode plate and the negative electrode plate, respectively, and superposed in order, with the long side parallel to the winding central axis of the power generating element with the rectangular core of polyethylene as the center. To form a power generating element having a size of 53 × 35 × 4 mm.

Then, the insulating portion of the electrode is covered with a winding tape made of polypropylene (here, an adhesive is applied on one side) to the width of the electrode (the length of the power generating element parallel to the winding central axis of the power generating element). Was attached to the side wall of the power generation element parallel to the winding center axis, and the power generation element was stopped and fixed.

This was housed in a metal-laminated resin film case so that the winding center axis of the elliptical wound type power generation element was perpendicular to the opening surface of the bag-shaped metal-laminated resin film case. Thereafter, each electrode and the short-circuit preventing film were sufficiently wetted by the vacuum injection of the electrolytic solution so that no free electrolytic solution was present outside the power generating element. To the electrolytic solution, LiPF ₆ was added at a concentration of 1 mol / L to a solvent in which ethylene carbonate and dimethyl carbonate were mixed at a weight ratio of 5: 5, and 0.01 to 0.1 mol of fluorobenzene was added.
Six types of batteries were manufactured using the ones added at the respective concentrations of 1, 1, 3, 15, and 30 wt%.

The laminated resin film uses a 12 μm PET film for surface protection as the outermost layer, a 9 μm aluminum foil as a barrier layer inside the PET film, and a 100 μm acid-modified low-density polyethylene layer as a heat welding layer as the innermost layer. . In this metal laminated resin film, the outermost PET film for surface protection and an aluminum foil as a barrier layer are bonded with a urethane-based adhesive. The positive electrode lead terminal and the negative electrode lead terminal have a thickness of 50 to 100.
It is a metal conductor of copper, aluminum, nickel or the like of μm.

Finally, a sealed unit cell (A) having a nominal capacity of 500 mAh according to the present invention was produced by sealing and welding. A comparative battery (B) was produced in the same manner as the battery (A) according to the present invention except that fluorobenzene was not added to the electrolytic solution.

All these batteries were manufactured at 25 ° C.
, After charging to 4.1 V with a constant current of 500 mA, and then performing constant-voltage charging at 4.1 V for 2 hours,
A high-rate discharge test was performed by discharging to 3.3 V at a constant current of 1,500 mA at 5 ° C. Furthermore, at 25 ° C., 5
After charging to 4.1 V at a constant current of 00 mA and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was discharged at -20 ° C. to a constant current of 500 mA to 3.3 V to perform a low-temperature discharge test. Table 1 shows the discharge capacities obtained at that time.

[0059]

[Table 1]

From Table 1, it can be seen that the battery according to the present invention in which fluorobenzene is added to the electrolyte has a higher capacity at high rate discharge and a lower capacity at low temperature discharge as compared with a comparative battery not using fluorobenzene. I understand. The concentration of fluorobenzene in the electrolyte is 0.01 wt.
% Was found to be particularly effective when the content was 15% by weight or more and 15% by weight or less.

Example 2 Example 1 was repeated except that, instead of adding fluorobenzene to the electrolytic solution, 23 kinds of halogen-bonded benzene compounds other than fluorobenzene were added to the electrolytic solution at a concentration of 3 wt%. 23 types of batteries (C) according to the present invention were manufactured in the same manner as the battery (A) according to the present invention.

[0062] All of these fabricated batteries were stored at 25 ° C.
, After charging to 4.1 V with a constant current of 500 mA, and then performing constant-voltage charging at 4.1 V for 2 hours,
A high-rate discharge test was performed by discharging to 3.3 V at 5 ° C. and a constant current of 1,500 mA. Furthermore, at 25 ° C., 5
After charging to 4.1 V at a constant current of 00 mA and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was discharged at -20 ° C. to a constant current of 500 mA to 3.3 V to perform a low-temperature discharge test. Table 2 shows a list of the halogen-bonded benzene compounds applied to the battery (C) and the discharge capacities obtained at that time.

[0063]

[Table 2]

From the comparison between Tables 1 and 2, it can be seen that all of the batteries (C) according to the present invention exhibited better high-rate discharge characteristics and lower-temperature discharge characteristics than the comparative battery (B). . In addition, it was found that when the halogen bonded to the benzene ring was fluorine, it exhibited excellent high-rate discharge characteristics and low-temperature discharge characteristics as compared with the case of chlorine or iodine. Furthermore, it was found that when the halogen-bonded benzene compound was fluorobenzene, it exhibited particularly excellent high-rate discharge characteristics and low-temperature discharge characteristics.

Example 3 Except that diethyl carbonate or methyl ethyl carbonate was used instead of dimethyl carbonate as the chain carbonate used in the electrolytic solution, 3 wt% of fluorobenzene was contained in the electrolytic solution.
A battery (D) according to the present invention was manufactured in the same manner as the battery (A) according to the present invention in Example 1 to which addition was made. Also,
A conventionally known comparative battery (E) was manufactured in the same manner as the battery (D) according to the present invention, except that no fluorobenzene was added to the electrolytic solution.

All of these batteries were manufactured at 25 ° C.
, After charging to 4.1 V with a constant current of 500 mA, and then performing constant-voltage charging at 4.1 V for 2 hours,
A high-rate discharge test was performed by discharging to 3.3 V at a constant current of 1,500 mA at 5 ° C. Furthermore, at 25 ° C., 5
After charging to 4.1 V at a constant current of 00 mA and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was discharged at -20 ° C. to a constant current of 500 mA to 3.3 V to perform a low-temperature discharge test. The discharge capacity obtained at that time is shown in Table 3 together with the results of the batteries (A) and (B) tested in Example 1. In addition, the battery (D) according to the present invention and the battery (E) for comparison, the battery (B) manufactured in Example 1, and the battery (A) in which the amount of fluorobenzene added to the electrolyte was 3 wt% were used. At 25 ° C.
The battery was charged to 4.1 V at a constant current of 500 mA, and further charged to 4.1 V.
After charging at constant voltage for 2 hours at 85 V,
Table 3 shows the amount of increase in battery thickness due to heating when heated for 3 hours.
Shown in

[0067]

[Table 3]

From Table 3, it can be seen that in a conventional battery not using a halogen-bonded benzene compound, when diethyl carbonate or methyl ethyl carbonate is used as the chain carbonate in the electrolytic solution, the high-rate discharge characteristics and the low-temperature discharge characteristics are inferior. Was.

From these problems, in order to obtain good high-rate discharge characteristics and low-temperature discharge characteristics, it was necessary to use dimethyl carbonate as the chain carbonate in the electrolytic solution. On the other hand, in the case of blistering when left at high temperatures,
As can be seen from Table 3, when dimethyl carbonate is used, swelling is more likely than when diethyl carbonate or methyl ethyl carbonate is used.

Therefore, conventionally, it has been difficult to manufacture a battery which is unlikely to swell when left at a high temperature in a charged state and has excellent discharge characteristics at a high rate or at a low temperature. From Table 3,
By combining the use of an electrolyte containing a halogen-bonded benzene compound with the use of diethyl carbonate or methyl ethyl carbonate for the electrolyte, it is unlikely to swell when left at high temperature in a charged state, and discharge at a high rate and low temperature It is understood that a battery having excellent characteristics can be manufactured.

Example 4 Except that a lithium nickel composite oxide or a lithium manganese composite oxide was used as the positive electrode active material instead of the lithium cobalt composite oxide, 3 wt% of fluorobenzene was added to the electrolytic solution. A battery (F) according to the present invention was manufactured in the same manner as the battery (A) according to the present invention in Example 1. Comparing the capacity per volume with the lithium cobalt composite oxide, the lithium nickel composite oxide has a large capacity and the lithium manganese composite oxide has a small capacity.

For this reason, even though batteries of the same size were manufactured, the batteries had a capacity of 530 mAh when the lithium nickel composite oxide was used and 455 mAh when the lithium manganese composite oxide was used. . Also,
A conventionally known comparative battery (G) was produced in the same manner as the battery (F) according to the present invention, except that no fluorobenzene was added to the electrolytic solution.

All of these batteries were manufactured at 25 ° C.
, After charging to 4.1 V with a constant current of 500 mA, and then performing constant-voltage charging at 4.1 V for 2 hours,
The battery was discharged to 3.3 V by a low-rate discharge of 100 mA at 5 ° C. Further, at 25 ° C., the battery was charged to 4.1 V at a constant current of 500 mA, and then was charged at 4.1 V for 2 hours, and then discharged at 25 ° C. to 3.3 V at a constant current of 1,500 mA. Rate discharge test was performed. 1,50 with respect to the capacity at the time of 100 mA discharge obtained at that time
Table 4 shows the capacity ratio at the time of 0 mA discharge together with the results of the batteries (A) and (B) manufactured in Example 1.

[0074]

[Table 4]

From Table 4, it was found that in a conventional battery not using a halogen-bonded benzene compound, when a lithium nickel composite oxide or a lithium manganese composite oxide was used as a positive electrode active material, high-rate discharge characteristics were inferior.
From these problems, in order to obtain good high-rate discharge characteristics, it was necessary to use a lithium-cobalt composite oxide as the positive electrode active material.

On the other hand, in terms of cost, lithium cobalt composite oxide is more expensive than lithium nickel composite oxide or lithium manganese composite oxide. Therefore, conventionally, it has been difficult to manufacture a battery that is inexpensive and has excellent high-rate discharge characteristics.

From Table 4, it can be seen that the combination of the use of an electrolyte containing a halogen-bonded benzene compound and the use of a lithium nickel composite oxide or a lithium manganese composite oxide as a positive electrode active material makes it possible to reduce the cost. It is understood that it is possible to manufacture a battery having excellent discharge characteristics at a high rate.

Example 5 The electrolyte solution was the same as that of the first embodiment except that the pores of the active material layers of the positive electrode and the negative electrode were filled with a polymer electrolyte having fine pores, and the amount of the electrolyte added was reduced by the volume. A battery (H) according to the present invention was manufactured in the same manner as the battery (A) according to the present invention in Example 1 in which 3 wt% of fluorobenzene was added to the battery. The filling of the polymer electrolyte having fine pores into the pores of the active material layers of the positive electrode and the negative electrode was performed as follows. Polyvinylidene fluoride (PVD
After filling a solution of F) in N-methylpyrrolidone into the pores of the active material layer, PVDF was made porous and solidified by a solvent extraction method in which the electrode was immersed in water. After drying the electrode, a battery was assembled. By injecting the electrolyte,
PVDF having fine pores in the pores of the active material layer swells,
It became a polymer electrolyte. In addition, a conventionally known comparative battery (I) was manufactured in the same manner as the battery (H) according to the present invention except that fluorobenzene was not added to the electrolytic solution.

All of these batteries were manufactured at 25 ° C.
, After charging to 4.1 V with a constant current of 500 mA, and then performing constant-voltage charging at 4.1 V for 2 hours,
A high-rate discharge test was performed by discharging to 3.3 V at a constant current of 1,500 mA at 5 ° C. Furthermore, at 25 ° C., 5
After charging to 4.1 V at a constant current of 00 mA and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was discharged at -20 ° C. to a constant current of 500 mA to 3.3 V to perform a low-temperature discharge test. The discharge capacity obtained at that time is shown in Table 5 together with the results of the batteries (A) and (B) tested in Example 1.

The battery (H) according to the present invention, the battery (I) for comparison, and the battery (B) manufactured in Example 1
And 3wt% of fluorobenzene added to electrolyte
500 m at 25 ° C. using the battery (A)
Table 5 shows the amount of increase in battery thickness due to heating when the battery was charged to 4.1 V with a constant current of A, and further charged at 4.1 V for 2 hours and then heated at 85 ° C. for 4 hours. .

[0081]

[Table 5]

From Table 5, it can be seen that in the conventional battery not using the halogen-bonded benzene compound, the high-rate discharge characteristics and the low-temperature discharge characteristics were obtained by filling the pores of the active material layers of the positive electrode and the negative electrode with a polymer electrolyte having fine pores. Was found to be inferior.

From the above problems, in order to obtain good high-rate discharge characteristics and low-temperature discharge characteristics, a polymer electrolyte cannot be used in the pores of the active material layers of the positive electrode and the negative electrode. . On the other hand, as can be understood from Table 5, when the polymer electrolyte is not left, the swelling when the polymer electrolyte is not used is swelled more easily than when the polymer electrolyte is used. Therefore, conventionally, it has been difficult to manufacture a battery that is unlikely to swell when left at a high temperature in a charged state and has excellent discharge characteristics at a high rate or at a low temperature.

From Table 5, it can be seen that the combination of using an electrolytic solution containing a halogen-bonded benzene compound and filling a polymer electrolyte having fine pores into the pores of the active material layers of the positive electrode and the negative electrode provides a charge. It is understood that it becomes possible to manufacture a battery which is less likely to swell when left at a high temperature in a state and has excellent discharge characteristics at a high rate and a low temperature.

Example 6 By changing the thickness of the active material layer, the thickness of the positive electrode and the negative electrode was reduced to 100, 12
0, 150, 200, 300, 400, 500, 600
except that fluorobenzene was added to the electrolyte.
Eight kinds of batteries (J) according to the present invention in the same manner as the battery (A) according to the present invention in Example 1 in which wt% was added.
Was made. The length of the electrode was changed according to the thickness of the electrode so that the wound element was housed in the same battery case. As a result, as the thickness of the electrode increases,
This resulted in a battery with a large capacity and a high energy density. A conventionally known comparative battery (K) was manufactured in the same manner as the battery (J) according to the present invention except that fluorobenzene was not added to the electrolytic solution.

[0086] All of these batteries were manufactured at 25 ° C.
, After charging to 4.1 V with a constant current of 500 mA, and then performing constant-voltage charging at 4.1 V for 2 hours,
The battery was discharged to 3.3 V by a low-rate discharge of 100 mA at 5 ° C. Further, at 25 ° C., the battery was charged to 4.1 V at a constant current of 500 mA, and then was charged at 4.1 V for 2 hours, and then discharged at 25 ° C. to 3.3 V at a constant current of 1,500 mA. Rate discharge test was performed. 1,50 with respect to the capacity at the time of 100 mA discharge obtained at that time
Table 6 shows the capacity ratio at the time of 0 mA discharge.

Further, by using these batteries, 500 m
After charging to 4.1 V with a constant current A and performing constant voltage charging at 4.1 V for 2 hours, discharging to 2.75 V with a constant current of 500 mA is defined as one cycle, and 100 cycles of charging at 25 ° C. Discharge occurred. Table 6 shows the ratio of the capacity at the 100th cycle to the capacity at the first cycle of the 100 cycles.

[0088]

[Table 6]

From Table 6, it was found that in the conventional battery using no halogen-bonded benzene compound, the higher the discharge rate, the lower the high-rate discharge characteristics. From such a problem, in order to obtain good high-rate discharge characteristics, the thickness of the electrode needs to be less than 120 μm. On the other hand, when the electrode becomes thin, the ratio of the error of the active material layer thickness to the active material layer thickness increases. Therefore, the error in the capacity ratio between the positive electrode and the negative electrode depending on the location of the electrode becomes large, so that metallic lithium is easily deposited on the negative electrode. Since lithium metal has a low charge / discharge high rate, there is a problem that the capacity is easily reduced by the charge / discharge cycle of the battery.

Therefore, conventionally, it has been difficult to manufacture a battery having excellent charge-discharge cycle characteristics and high-rate discharge characteristics. From Table 6, it can be seen that the electrolyte containing the halogen-bonded benzene compound was used, and that the thickness of the electrode was 120
It is understood that a combination of the thicknesses of not less than μm makes it possible to manufacture a battery having excellent charge-discharge cycle characteristics and excellent discharge characteristics at a high rate. From Table 6, it was found that when the electrode thickness exceeded 500 μm, practical high-rate charge / discharge characteristics could not be obtained.

[Example 7] The porosity of the short-circuit preventing film was set to 2
Except that 5, 30, 40, 50, 60, 65, and 70% were used, 3% by weight of fluorobenzene was added to the electrolytic solution in the same manner as in the battery (A) according to the present invention in Example 1 to obtain 8% of the present invention. Various types of batteries (L) were manufactured. A conventionally known comparative battery (M) was manufactured in the same manner as the battery (L) according to the present invention except that fluorobenzene was not added to the electrolytic solution. All of these batteries were manufactured in 10 units.

All of these batteries were manufactured at 25 ° C.
After charging to 4.1 V at a constant current of 500 mA and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was left at room temperature for 3 days to check the voltage drop during that time. Checked the number. Table 7 shows the results. A high-rate discharge test was performed by using each of the batteries that had not been internally short-circuited in this test and discharging the battery to 3.3 V at a constant current of 1,500 mA at 25 ° C. Further, the battery was charged to 4.1 V at a constant current of 500 mA at 25 ° C., and then charged at a constant voltage of 4.1 V for 2 hours, and then 3.3 V at a constant current of 500 mA at −20 ° C.
And a low-temperature discharge test was performed. Table 7 shows the discharge capacities obtained at that time.

[0093]

[Table 7]

From Table 7, it was found that in the conventional battery using no halogen-bonded benzene compound, as the porosity of the short-circuit preventing film became lower, the high-rate discharge characteristics and the discharge characteristics at low temperatures were inferior. From such a problem, in order to obtain good high-rate discharge characteristics, it is necessary to make the porosity of the short-circuit preventing film higher than 65%.

On the other hand, when the porosity of the short-circuit preventing film is increased, there is a problem that the mechanical strength of the film is weakened and an internal short-circuit is likely to occur. Therefore, conventionally, it has been difficult to manufacture a battery in which an internal short circuit hardly occurs and which has excellent high-rate discharge characteristics.

From Table 7, it can be seen that the use of the electrolytic solution containing the halogen-bonded benzene compound and the porosity of
It is understood that the combination of the content of 5% or less makes it possible to produce a battery which is less likely to cause an internal short circuit and has excellent discharge characteristics at a high rate. In addition,
From Table 7, it was found that when the porosity of the short-circuit preventing film was less than 30%, practical high-rate charge / discharge characteristics could not be obtained.

[Example 8] The average pore size of the short-circuit preventing film was set to 0.
005, 0.01, 0.1, 1, 3, 5 μm according to the present invention in the same manner as the battery (A) according to the present invention in Example 1 in which 3 wt% of fluorobenzene was added to the electrolytic solution. Six types of batteries (N) were manufactured. In addition, a conventionally known comparative battery (O) was manufactured in the same manner as the battery (N) according to the present invention except that no fluorobenzene was added to the electrolytic solution. All of these batteries were manufactured in 10 units.

[0098] All of these batteries were manufactured at 25 ° C.
After charging to 4.1 V at a constant current of 500 mA and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was left at room temperature for 3 days to check the voltage drop during that time. Checked the number. Table 8 shows the results. A high-rate discharge test was performed by using each of the batteries that had not been internally short-circuited in this test and discharging the battery to 3.3 V at a constant current of 1,500 mA at 25 ° C. Further, the battery was charged to 4.1 V at a constant current of 500 mA at 25 ° C., and then charged at a constant voltage of 4.1 V for 2 hours, and then 3.3 V at a constant current of 500 mA at −20 ° C.
And a low-temperature discharge test was performed. Table 8 shows the discharge capacities obtained at that time.

[0099]

[Table 8]

From Table 8, it was found that in the conventional battery not using the halogen-bonded benzene compound, as the average pore diameter of the short-circuit preventing film became smaller, the high-rate discharge characteristics and the low-temperature discharge characteristics were inferior. Because of these problems,
In order to obtain good high-rate discharge characteristics, it was necessary to make the average pore diameter of the short circuit prevention film larger than 3 μm. On the other hand, when the average pore diameter of the short-circuit prevention film is large, there is a problem that the dropped active material particles easily enter the pores, and an internal short circuit is easily generated. Therefore, conventionally, it has been difficult to manufacture a battery in which an internal short circuit hardly occurs and which has excellent high-rate discharge characteristics.

From Table 8, it can be seen that the combination of the use of an electrolyte containing a halogen-bonded benzene compound and the reduction of the average pore diameter of the short-circuit prevention film to 3 μm or less makes it difficult for internal short-circuits to occur and to discharge at a high rate. It is understood that a battery having excellent characteristics can be manufactured. From Table 8, it was found that when the average pore diameter of the short-circuit prevention film was less than 0.01 μm, practical high-rate charge / discharge characteristics could not be obtained.

Example 9 The average particle size of the primary particles was 0.1%.
2-0.4, 0.5-0.8, 1-4, 5-8, 10
Except that a positive electrode active material having a size of 15, 20 to 30, 35 to 50 μm was used, fluorobenzene was added to the electrolyte solution in 3w.
Battery (A) according to the invention in Example 1 with addition of t%
In the same manner as in the above, seven types of batteries (P) according to the present invention were produced. A conventionally known comparative battery (Q) was manufactured in the same manner as the battery (P) according to the present invention except that fluorobenzene was not added to the electrolytic solution.

[0103] All of these batteries were manufactured at 25 ° C.
, After charging to 4.1 V with a constant current of 500 mA, and then performing constant-voltage charging at 4.1 V for 2 hours,
A high-rate discharge test was performed by discharging to 3.3 V at a constant current of 1,500 mA at 5 ° C. Furthermore, at 25 ° C., 5
After charging to 4.1 V at a constant current of 00 mA and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was discharged at -20 ° C. to a constant current of 500 mA to 3.3 V to perform a low-temperature discharge test. Table 9 shows the discharge capacities obtained at that time. Further, the battery (P) according to the present invention and the battery (Q) for comparison were charged at 25 ° C. at a constant current of 500 mA to 4.1 V, and further charged at 4.1 V for 2 hours at a constant voltage. Later, when heated at 85 ° C. for 4 hours,
Table 9 shows the increase in battery thickness due to heating.

[0104]

[Table 9]

From Table 9, it was found that in the conventional battery not using the halogen-bonded benzene compound, the high-rate discharge characteristics and the low-temperature discharge characteristics were inferior when the particle diameter of the primary particles of the positive electrode active material was increased. From these problems, in order to obtain good high-rate discharge characteristics and low-temperature discharge characteristics, it is necessary to make the particle diameter of primary particles of the positive electrode active material less than 0.5 μm.

On the other hand, in the case of blistering when left at high temperature, Table 9
As will be understood from the above, the primary particles of the positive electrode active material tend to swell as the particle diameter becomes smaller. Therefore, conventionally, it has been difficult to manufacture a battery that is unlikely to swell when left at a high temperature in a charged state and has excellent discharge characteristics at a high rate or at a low temperature.

From Table 9, it can be seen that the combination of the use of the electrolyte containing the halogen-bonded benzene compound and the setting of the primary particles of the positive electrode active material having a particle diameter of 0.5 μm or more allows the high-temperature storage in a charged state. It is understood that it is possible to manufacture a battery that is less likely to swell and has excellent high-rate and low-temperature discharge characteristics.

From Table 9, it was found that when the particle size of the primary particles of the positive electrode active material was larger than 30 μm, practical high-rate charge / discharge characteristics could not be obtained.

Example 10 The average particle size of primary particles was 1
２2, 3 to 10, 15 to 25, 30 to 50, 60 to 70
Except that a negative active material having a thickness of μm was used, the same method as in the battery (A) according to the present invention in Example 1 except that 3 wt% of fluorobenzene was added to the electrolytic solution was used.
Types of batteries (R) were produced. When the negative electrode active material was large, the active material was crushed and deformed during pressing. Also,
A conventionally known comparative battery (S) was manufactured in the same manner as the battery (R) according to the present invention, except that no fluorobenzene was added to the electrolytic solution.

[0110] All of these batteries were manufactured at 25 ° C.
, After charging to 4.1 V with a constant current of 500 mA, and then performing constant-voltage charging at 4.1 V for 2 hours,
A high-rate discharge test was performed by discharging to 3.3 V at a constant current of 1,500 mA at 5 ° C. Furthermore, at 25 ° C., 5
After charging to 4.1 V at a constant current of 00 mA and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was discharged at -20 ° C. to a constant current of 500 mA to 3.3 V to perform a low-temperature discharge test. Table 10 shows the discharge capacities obtained at that time. Using the battery (R) according to the present invention and the battery (S) for comparison, the battery was charged at 25 ° C. at a constant current of 500 mA to 4.1 V, and further charged at 4.1 V for 2 hours at a constant voltage. Table 10 shows the amount of increase in battery thickness due to heating when heated at 85 ° C. for 4 hours.

[0111]

[Table 10]

From Table 10, it was found that in the conventional battery not using the halogen-bonded benzene compound, when the primary particles of the negative electrode active material had a large particle diameter, the high-rate discharge characteristics and the low-temperature discharge characteristics were inferior. Because of these problems,
In order to obtain good high-rate discharge characteristics and low-temperature discharge characteristics, the primary particles of the negative electrode active material had to have a particle diameter of less than 3 μm.

On the other hand, in the case of blistering when left at high temperature, Table 1
As can be understood from FIG. 0, the primary particles of the negative electrode active material tend to swell as the particle size decreases. Therefore, conventionally, it has been difficult to manufacture a battery that is unlikely to swell when left at a high temperature in a charged state and has excellent discharge characteristics at a high rate or at a low temperature.

From Table 10, it can be seen that the combination of the use of the electrolytic solution containing the halogen-bonded benzene compound and the setting of the primary particles of the negative electrode active material having a particle diameter of 3 μm or more makes it hard to swell when left at high temperature in a charged state. It can be understood that a battery having excellent discharge characteristics at high rate and low temperature can be manufactured.

From Table 10, it was found that when the particle size of the primary particles of the negative electrode active material was larger than 50 μm, practical high-rate charge / discharge characteristics could not be obtained.

[Example 11] An electrolyte solution containing no fluorobenzene was injected and charged with a quantity of electricity of 200 mAh, and then the concentration of fluorobenzene in the electrolyte solution was reduced to 3 watts.
A battery (T) according to the present invention was manufactured in the same manner as the battery (A) according to the present invention in Example 1 in which 3 wt% of fluorobenzene was added to the electrolytic solution, except that fluorobenzene was added so as to be t%. did.

This battery was charged to 500 mA at 25 ° C.
After charging to 4.1 V with a constant current, and then performing constant voltage charging at 4.1 V for 2 hours, 1,500 mA at 25 ° C.
A high-rate discharge test was performed by discharging to 3.3 V at a constant current. Further, at 25 ° C. and 500 mA constant current, 4.
After charging to 1 V and then performing constant-voltage charging at 4.1 V for 2 hours, the battery was discharged at −20 ° C. at a constant current of 500 mA to 3.3 V to perform a low-temperature discharge test. The discharge capacity obtained at that time is shown in Table 11 together with the result of the battery (A) according to the present invention.

[0118]

[Table 11]

From Table 11, it can be seen that when the halogen-bonded benzene compound was added to the battery after the charging step, an even higher rate was obtained as compared with the case where the halogen-bonded benzene compound was added before the charging step. It was found that the battery exhibited discharge characteristics and discharge characteristics at a low temperature.

In a non-aqueous electrolyte battery provided with a negative electrode provided with carbon, a film is formed on the carbon surface at the time of the first charge, so that subsequent decomposition of the electrolytic solution at the negative electrode is suppressed. However, when a halogen-bonded benzene compound is added to the electrolytic solution, the ion permeability of the film formed on the surface of the carbon negative electrode slightly decreases.

Therefore, by performing a charging process using an electrolyte solution containing no halogen-bonded benzene compound, a film having high ion permeability is formed on the carbon surface, and then the halogen-bonded benzene compound is added into the battery. In addition, it is possible to suppress a decrease in ion permeability of the film. As a result, a non-aqueous electrolyte having particularly excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics can be manufactured by this manufacturing method.

[0122]

According to the present invention, by adding a halogen-bonded benzene compound to the electrolytic solution, a non-aqueous electrolyte battery having excellent high-rate charge / discharge characteristics and low-temperature charge / discharge characteristics can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) CJ16 DJ08 EJ11 HJ05 HJ10

Claims (7)

[Claims] At least one halogen and a substituent other than a halogen are bonded to a benzene ring, and an atom bonded to the benzene ring of the substituent other than the halogen is carbon, nitrogen,
A non-aqueous electrolyte battery comprising a compound selected from the group consisting of sulfur in the electrolytic solution. 2. The non-halogen substituent is one selected from the group consisting of an alkyl group, a cyan group, a nitro group, an amino group, a sulfone group, a carbonyl group, a carboxyl group, and an aldehyde group. The non-aqueous electrolyte battery according to claim 1. 3. The non-aqueous electrolyte battery according to claim 1, wherein the halogen is fluorine. 4. The non-aqueous electrolyte battery according to claim 1, wherein the compound is fluorobenzene. 5. A compound having a concentration of 0.01 w in an electrolyte.
5. The nonaqueous electrolyte battery according to claim 1, wherein the content is at least t% and at most 15 wt%. 6. The particle diameter of primary particles is 0.5 μm or more and 30 or more.
The positive electrode active material or the primary particles having a particle size of 3 μm or less
The nonaqueous electrolyte battery according to claim 1, further comprising a negative electrode active material having a size of not less than 50 μm and not more than 50 μm. 7. A method for producing a non-aqueous electrolyte battery provided with carbon on a negative electrode, wherein after the charging step, a compound having at least one halogen bonded to a benzene ring is added to the battery. A method for manufacturing a non-aqueous electrolyte battery.