JP5763889B2 - Non-aqueous electrolyte secondary battery charge / discharge method - Google Patents

Description

The present invention relates to a charge / discharge method for a non-aqueous electrolyte secondary battery.

Lead acid batteries are used in automobile starters. Lead-acid batteries are widely used as backup power sources for various industrial and business purposes. At present, there is a strong movement to replace the lead storage battery used in the backup power source with a nickel metal hydride battery or a lithium ion battery. The main reasons for this are the desire to reduce the size of the power supply by replacing it with a battery with a higher energy density than the lead-acid battery, and the use of a clean battery instead of a battery that uses lead in terms of environmental impact. There is a demand.
There is no major move to replace lead-acid batteries used in automobiles. However, it is desirable to replace the battery with a clean battery from the viewpoint of environmental load. In consideration of use in automobiles, it may be desirable to substitute a lithium ion battery that is lighter and more advantageous than a nickel metal hydride battery. In view of the above, it will become necessary in the future to substitute for lithium ion batteries in the field of automobiles and backup power supplies in which lead storage batteries are currently used.

Lithium ion batteries used as the main power source for mobile communication devices and portable electronic devices
It has the feature of having high electromotive force and high energy density. As the positive electrode active material used here, lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ )
, Manganese spinel (LiMn ₂ O ₄ ), and mixtures thereof. These positive electrode active materials have a voltage of 4 V or more with respect to lithium.
In addition, a carbon material is generally used for the negative electrode.
A class V lithium ion battery is constructed. Considering alternatives to lead-acid batteries, lithium-ion batteries having the same voltage and lithium-ion batteries having a voltage multiple of 6 when a plurality are connected in series are desired. In this sense, a 4V class battery is not suitable. A lithium ion battery with a voltage of 2V or 3V would be convenient as an alternative. Various means for reducing the voltage are conceivable. Since the present invention is characterized by using titanium oxide for the negative electrode, the prior art will be described focusing on this system.

Patent Document 1 includes a negative electrode containing spinel-type lithium-titanium oxide (Li _4/3 Ti _5/3 O ₄ ) as an active material, a positive electrode containing Li ₂ MnO ₃ or LiMnO ₂ as an active material,
A non-aqueous electrolyte lithium secondary battery comprising a non-aqueous electrolyte is disclosed. However, the actual discharge voltage is around 1.6V, which is low for a 2V battery.
Patent Document 2 _discloses an active material containing spinel-type lithium-manganese oxide Li _4/3 Mn _5/3 O ₄ using spinel-type lithium-titanium oxide as the negative electrode active material. A non-aqueous electrolyte secondary battery used for a positive electrode is disclosed. This battery system has a voltage around 2.5V and a slightly higher voltage for a 2V battery, but may be a preferred voltage. However, the problem that Mn is eluted from the spinel type lithium manganese oxide and the deterioration due to storage and the cycle life is low have not been solved essentially.

Patent Document 3 discloses a battery using lithium cobaltate (LiCoO ₂ ) as a positive electrode active material and Li _4/3 Ti _5/3 O ₄ lithium titanate as a negative electrode active material. This battery system also has a preferable battery voltage, but increases the cost because a large amount of Co metal is used. As will be described later, since LiCoO ₂ repeats volume expansion and contraction with charge and discharge, the crystal lattice is easily broken, and it is expected that there will be a problem in terms of long-term reliability.
In Patent Document 4, LiA _x B _1-x O ₂ (A and B are metallic elements Co, N
lithium transition metal oxide represented by i, Mn, Fe, V, Al or Ti), lithium titanium oxide represented by Li _4/3 Ti _5/3 O ₄ as the negative electrode active material, and lithium A lithium secondary battery in which the ratio of the actual capacity of the lithium titanium oxide to the actual capacity of the transition metal oxide is 0.5 or less is disclosed. The invention described in Patent Document 4 mainly relates to battery design that focuses on the capacity balance between the positive and negative electrodes, and there is no description regarding the necessity of a combination that takes advantage of the characteristics of individual materials as described later.

In Patent Document 5, in a battery system using a titanium ion deficient Li _4/3 Ti _5/3 O ₄ which is a spinel type lithium titanium oxide as a negative electrode, carbon, graphite, WO ₂ , Fe ₂ O ₃ , LiF
It is disclosed that e ₅ O ₈ , SiO ₂ and SnO are added. The present invention aims to improve the overdischarge resistance and overcharge resistance characteristics, and is different in configuration and purpose from the present invention.
Patent Document _{6, Li 1 + x M y} Mn 2-xy O 4-z (M is Ti, V, Cr, Fe, Co, Ni
, Zn, Cu, W, Mg, Al, one or more, 0 ≦ x ≦ 0.2, 0 ≦ y <0.5, 0 ≦
z <0.2), and the full width at half maximum of the (400) diffraction peak by the powder X-ray diffraction method using CuKα rays is 0.02θ or more and 0.1θ or less (θ is the diffraction angle), A lithium manganese composite oxide having an octahedral shape is disclosed as a positive electrode active material. Then, the negative electrode including a positive electrode including the positive electrode active material, the _{Li a Ti b O 4 (0.5} ≦ a ≦ 3,1 ≦ b ≦ 2.5) lithium-titanium composite oxide represented by a negative electrode active material Has been proposed. This battery system exhibits a discharge voltage of 3V or more, which is slightly different from the voltage of the battery according to the present invention.

Patent Document _{7, Li 1-x A x Ni} 1-y M y O 2 (A is an alkali metal except Li, 1 or more selected from alkaline earth metals; M is Co, Mn, Al, Cr , Fe, V, Ti, Ga
1 or more selected from the above; 0 ≦ x ≦ 0.2; 0.05 ≦ y ≦ 0.5), and the primary particles are aggregated to form secondary particles. The formed lithium nickel composite oxide is disclosed as a positive electrode active material. And the positive electrode containing this positive electrode active material, and L
i _a Ti _b O ₄ battery comprising a negative electrode containing (0.5 ≦ a ≦ 3,1 ≦ b ≦ 2.5) lithium-titanium composite oxide represented by a negative active material is disclosed. An object of the present invention is to provide a lithium secondary battery that is inexpensive and has good cycle characteristics, in particular, cycle characteristics in high-temperature storage and high-temperature storage characteristics.
For this purpose, the invention described in Patent Document 7 focuses on the following two points. First,
In the present invention, the average particle diameter of the primary particles of the positive electrode active material needs to be 0.5 μm or more. Regarding the basis of this idea, also in the text, the primary particles are particles close to a single crystal, and it is difficult to avoid expansion / contraction, that is, volume change due to lithium insertion / extraction due to repeated charge / discharge. As described, there is an essentially unavoidable volume change. In order to alleviate this, it has been proposed to increase the primary particle size.

Regarding the composition of transition metal species, etc., it is described that Co, Mn, Al, etc. are added for the purpose of suppressing the phase change from the hexagonal system to the monoclinic system of the crystal structure. It is known and not a special technique. Furthermore, there is a description that by adding Al, the decomposition reaction of the active material accompanied by the release of oxygen is suppressed, and the thermal stability is improved and the electron conductivity is improved at the same time. It is. For example, Non-Patent Document 1 and Patent Document 8 include LiNiO.
It is described that a part of Ni in ₂ is replaced with Co to suppress a change in crystal phase. Further, Non-Patent Document 2 and Patent Document 9 describe that thermal stability is improved by adding Al.
Second, it has been proposed to use a lithium titanium oxide represented by Li _a Ti _b O ₄ (0.5 ≦ a ≦ 3, 1 ≦ b ≦ 2.5) as the negative electrode active material. Thereby, the reduction potential is Li / L.
Since it is 1.5V with respect to i +, which is higher than commonly used carbon materials, it is possible to suppress the decomposition of the non-aqueous electrolyte, and to the accompanying negative electrode surface of reactive organisms It is described that the precipitation / adhesion of the metal is suppressed and the cycle life is improved. However, the high potential is clearly shown in the above-described prior art of titanium oxide, and is not newly provided by the present invention.

Finally, regarding the combination of the positive electrode and the negative electrode in the battery, there is no description that a new effect is produced by the combination described in Patent Document 7, the effect of each of the positive electrode and the negative electrode is described individually, and the combination of simple effects is described It is merely a matter that can be easily inferred from the prior art. Also, as shown in the examples, copper is used as the negative electrode core, a thin microporous membrane is used as the separator, and currently used solvents and solutes are disclosed as the electrolyte. Yes. All of these are used for lithium secondary batteries currently on the market or are known ones. Moreover, there is no description that a new effect is exhibited by specifically selecting them.

Japanese Patent Application Laid-Open No. 07-320784 Japanese Patent Laid-Open No. 10-027609 JP 07-335261 A Japanese Patent Laid-Open No. 10-027626 Japanese Patent Laid-Open No. 10-069922 JP 2001-210324 A Japanese Patent Laid-Open No. 2001-243952 Japanese Patent Laid-Open No. 09-171824 JP-A-10-208744

T. Ohzuku et al., J. Elecrtochem. Soc., 140, 1862 (1993) T. Ohzuku et al., J. Elecrtochem. Soc., 142, 4033 (1995)

In recent years, there has been a strong demand for improving high rate characteristics and pulse characteristics. Charging / discharging at a high rate increases the load on the material, and as a result, the conventional technology does not improve the structural breakdown and the like, and it is difficult to maintain the cycle life. In addition, lithium cobaltate and graphite materials having a layer structure are repeatedly expanded and contracted in the layer direction along with charge / discharge, and therefore, particularly due to material stress due to this and oozing of electrolyte solution between the electrodes. There was a problem that the cycle life in charge and discharge was short. Therefore, suppressing the expansion and contraction of the battery system is a major element for solving the problem of extending the life.
Then, one of the objectives of this invention is providing the battery system which can suppress the volume expansion accompanying charging / discharging theoretically to substantially zero. Therefore, not only the positive and negative active materials but also the combination of positive and negative electrodes is important.

In the field of automobiles and backup power supplies where lead batteries are currently used, it will be necessary to replace them with lithium ion batteries in the future. Therefore, the present invention simultaneously provides a battery system that can provide an appropriate voltage for these applications. This makes it possible to reduce the size and weight. A suitable voltage is the same 2V discharge voltage as a lead battery. Furthermore, as a power supply for idling stop, it is desirable to keep the state of charge of the battery at, for example, about 60% to 70%. This is suitable when considering the control for performing regenerative charging. In order to facilitate such control, the battery voltage should change relatively linearly in this region. In the present invention, as will be described later in the embodiment, when discharging, that is, in a region where the battery capacity is 50% or less, a flat discharge voltage is maintained so that a constant voltage of 2V can be supplied, and in a region where the battery capacity is 60% or more, charging is performed. An object of the present invention is to provide a battery system in which the voltage increases linearly with charging so that the control is easy. There is no proposal from this viewpoint in the prior art.

In the present invention, extensive research has been conducted on electrolytes. Solvents that cannot be used due to reductive decomposition when using conventional carbon materials include solvents with high oxidation resistance and solvents with high flash points. We also propose that these can be used to dramatically improve the safety and reliability of batteries. In particular, a great effect can be expected by using an ionic liquid. Since ionic liquids do not have vapor pressure, the risk of battery ignition and smoke is extremely low. As for the separator, currently used olefinic microporous membranes such as polyethylene and polypropylene can be used. However, there is a problem that these separators are expensive.
A battery is a combination of a positive electrode and a negative electrode, and the balance of the capacity ratio between the positive electrode and the negative electrode has a great influence on battery characteristics, particularly cycle life and long-term reliability. This design know-how is also intensively studied in the present invention, and a preferable range is proposed.

As a negative electrode current collector, copper is generally used, but copper has a large specific gravity and is inferior in weight efficiency. Furthermore, there is a problem that when the electric potential exceeds 3 V on the basis of lithium metal during deep discharge, elution occurs. In addition, when overcharged, lithium ions are deposited in the form of needles as metallic lithium, and there is a problem that safety is significantly lowered. However, because a carbon material is used for the negative electrode, copper metal had to be used. On the other hand, the combination of the present invention can reduce the weight by using aluminum or an aluminum alloy for the negative electrode core material, and further suppresses lithium precipitation by occlusion of lithium during overcharge, thereby significantly increasing safety. Can be prevented.

The present invention comprises a positive electrode including a positive electrode active material having a layer structure, a negative electrode including a titanium oxide having a spinel structure as a negative electrode active material, and a non-aqueous electrolyte, wherein the positive electrode active material is Li ₁ ± _x. Including at least one of Ni _1/2 Co _1/2 O ₂ (x ≦ 0.1) and Li ₁ ± _x Ni _1/3 Co _1/3 Mn _1/3 O ₂ (x ≦ 0.1), The titanium oxide is Li ₄ Ti ₅ O ₁₂ , the positive electrode and the negative electrode each include a current collector made of aluminum or an aluminum alloy, and the weight of the negative electrode active material with respect to the weight of the positive electrode active material Charge / discharge of a non-aqueous electrolyte secondary battery having a ratio of 0.5 or more and less than 1.2, such that the utilization rate of the positive electrode active material is 60% or less. Provide a method.

Further, the positive electrode active material is Li _{1 ± x} Ni _1/2 Co _1/2 O ₂ (x ≦ 0.1) and Li _{1 ± x} Ni _1.
It is preferable to contain at least one of _{/ 3} Co _1/3 Mn _1/3 O ₂ (x ≦ 0.1).
The error in the ratio between the nickel element and the cobalt element is preferably within 10 atomic%.
It is preferable that the positive electrode active material contains at least one selected from the group consisting of Al, Mg, St, Ca, Y, and Yb as an additive element.
It is preferable that the titanium oxide has a spinel structure.
The titanium oxide is preferably Li ₄ Ti ₅ O ₁₂ .

In addition, the non-aqueous electrolyte includes , as a solvent, ethylene carbonate, propylene carbonate, γ butyl lactone, γ valerolactone, methyl diglyme, sulfolane, trimethyl phosphate, triethyl phosphate, methoxymethyl ethyl carbonate, and fluorinated ethylene carbonate. It is preferable to include at least one selected from the group consisting of:

Further, the nonaqueous electrolyte preferably contains at least one ionic liquid.
As the cation of the ionic liquid, it is preferable to use a cation selected from the group consisting of imidazolium, pyridinium, phosphonium, ammonium, pyrrolidinium, guanidinium and isouronium.
The anion of the ionic liquid is preferably selected from the group consisting of halogen, sulfate, sulfonate, amide, imide, methane, borate, phosphate, antimonate, decanate, and cobalt tetracarbonyl.

The nonaqueous electrolyte secondary battery according to the present invention preferably includes a separator made of a nonwoven fabric. The separator is preferably composed of at least one selected from the group consisting of polyethylene, polypropylene, vinylon, nylon, polyethylene terephthalate, aramid resin, and polybutylene terephthalate.
The ratio of the capacity of the negative electrode active material to the capacity of the positive electrode active material is 0.5 or more and 1.2.
Is preferably less than.

It is preferable that the positive electrode and the negative electrode each include a current collector made of aluminum or an aluminum alloy.
It is preferable that the positive electrode active material is composed of crystal particles having a particle size of 0.1 to 8 μm and secondary particles of the crystal particles having a particle size of 2 to 30 μm.
The negative electrode active material is preferably composed of secondary particles having an average particle size of 10 μm or less formed by aggregating primary particles having an average particle size of 0.6 μm or less.

According to the present invention, the life deterioration due to volume expansion of the non-aqueous electrolyte secondary battery which has been a problem conventionally dramatically improved, it is possible to improve the cycle life.

It is a figure which shows the charging / discharging behavior of a lithium titanium oxide negative electrode. It is a figure which shows the volume change accompanying charging / discharging of a lithium titanium oxide negative electrode. It is a figure which shows the charging / discharging behavior of Li _{1 ± x} Ni _1/2 Co _1/2 O ₂ . Li ₁ is a diagram showing a charge-discharge behavior of _{± x Ni 1/3 Co 1/3 Mn 1/3} O 2. Li ₁ is a diagram showing a volume change accompanying the charge and discharge of the _{± x Ni 1/2 Co 1/2 O 2} . Li ₁ is a diagram showing a volume change accompanying the charge and discharge of the _{± x Ni 1/3 Co 1/3 Mn 1/3} O 2. It is a SEM photograph which shows the particle form of positive electrode material. It is another SEM photograph which shows the particle form of positive electrode material. Li ₁ is a superimposed view of the charging and discharging behavior of _{± x Ni 1/3 Co 1/3 Mn 1/3} O 2 and Li ₄ Ti ₅ O _12. It is a figure which shows the charging / discharging behavior of a battery. It is a figure showing the chemical composition of an ionic liquid. It is a figure showing the chemical composition of an ionic liquid. It is a figure showing the chemical composition of an ionic liquid. Li ₁ is a diagram showing a die rate meter measurement of _{± x Ni 1/2 Co 1/2 O 2} / Li 4 Ti 5 O 12 battery. It is another diagram showing a die rate meter measurement of _{Li 1 ± x Ni 1/2 Co 1/2} O 2 / Li 4 Ti 5 O 12 battery. It is a schematic longitudinal cross-sectional view of the cylindrical battery produced in the present Example.

(1) Synthesis of active material in the present invention Titanium oxide having a spinel structure that can be suitably used as a negative electrode active material is L
If i ₄ Ti ₅ O _12, since it is mounted on the already currently commercially available batteries can be purchased from high quality. Further, lithium carbonate or lithium hydroxide as a lithium compound and titanium oxide as a titanium source are mixed so as to have a target material composition, and about 800 ° C. to 1100 ° C. in an oxidizing atmosphere such as in the air or in an oxygen stream. By firing at a temperature of
It can also be easily synthesized.

The synthesis of the positive electrode active material is described below. Li _{1 ± α} [Me] O ₂ (0 ≦ α <0.2,
Me is at least one selected from the group consisting of Ni and Mn, Fe, Co, Ti and Cu.
Regarding the synthesis of transition metals including seeds, oxides, hydroxides and / or carbonates containing elements constituting the desired positive electrode active material are mixed and fired to have a predetermined composition. Can be synthesized. However, in this case, make the particle size of each material the same,
Thorough mixing is required to make the reaction uniform, and synthesis requires sophisticated powder technology.

In the present invention, a positive electrode active material synthesized by coprecipitating transition metals such as nickel, cobalt, and manganese as hydroxides or carbonates in an aqueous solution can also be used.
In this case, since nickel and manganese that are difficult to disperse are uniformly dispersed in the particles in advance, the synthesis is relatively easy. In an example relating to synthesis described later, a eutectic material was used as a hydroxide. Moreover, lithium hydroxide was used as a lithium source. Although these materials are sufficiently mixed and baked, they can be reacted more reliably by molding them into pellets.

Here, the value of α will be described. The value of α is a factor that is varied to control grain growth. When the value of α is decreased with respect to 1 of the stoichiometric composition, particle growth during synthesis can be suppressed, and the surface area tends to increase. Conversely, increasing the value of α can promote particle growth. Therefore, the particles are usually designed according to the required characteristics required for the battery, but the design of the particles can be controlled by changing the composition ratio of lithium. The fluctuation range of the value of α is substantially about ± 0.2, and if the fluctuation width becomes larger than this, the function of the original active material is impaired.

When the electrochemical measurement of the positive electrode active material was modeled, a cell for electrochemical measurement was produced as follows. That is, 80 parts by weight of the positive electrode active material, 10 parts by weight of acetylene black as a conductive agent, and 10 parts by weight of PVdF (polyvinylidene fluoride) as a binder are mixed and diluted with NMP (N-methyl-2-pyrrolidone). Then, the obtained mixture was applied onto an aluminum foil current collector. The current collector after application was dried in vacuum at 60 ° C. for 30 minutes, then cut to 15 × 20 mm ² and further dried in vacuum at 150 ° C. for 14 hours to obtain an electrode. The thickness of the obtained electrode was 120 μm to 190 μm. The counter electrode was obtained by pressure bonding a lithium metal sheet on a stainless steel plate. The separator is a polyethylene porous film,
As the electrolytic solution, a solution obtained by dissolving LiPF ₆ at 1.0 M in a solvent in which EC (ethylene carbonate) and DMC (dimethyl carbonate) were mixed at a volume ratio of 3 to 7 was used. The charging / discharging of the test single cell thus obtained was repeated between predetermined voltage regions at a current density of 0.17 mA / cm ² .

(2) Volume change of electrode in battery according to the present invention Suppressing expansion / contraction of the positive electrode and the negative electrode due to charging / discharging is a major factor for solving the problem of extending the life of the battery. One of the objects of the present invention is to provide a battery system that can theoretically suppress the volume expansion of an electrode accompanying charge / discharge to almost zero.
First, the volume change of the titanium oxide that is the negative electrode active material will be described. Fig. 1 shows Li ₄ Ti ₅
The charge / discharge curve of O ₁₂ is shown. From FIG. 1, it can be seen that this material exhibits an almost completely flat charge / discharge curve with respect to lithium metal at a potential of 1.55V. The change of the X-ray diffraction pattern accompanying charging / discharging is shown in FIG. The peak of the X-ray diffraction pattern is crystal system Fd3m, and a
= 8.370 ± 0.005, and it can be seen that the negative electrode theoretically has no volume change in the charge / discharge region.

3 and 4, Li _{1 ± x} Ni _1/2 Co _1/2 O ₂ (x ≦ 0.1), which is a positive electrode active material, respectively.
And a charge / discharge curve of Li _{1 ± x} Ni _1/3 Co _1/3 Mn _1/3 O ₂ (x ≦ 0.1) was shown. These materials are charged and discharged in a potential region almost similar to the well-known lithium nickel oxide, and show an average voltage of about 3.6 V on the basis of lithium metal. Therefore, it can be clearly seen from FIGS. 1, 3 and 4 that the battery system using a combination of titanium oxide and these nickel lithium oxides has a charge / discharge potential of 2V.
5 and 6 show the volume change of the positive electrode active material accompanying charge / discharge similarly calculated from the X-ray diffraction method. 5 and 6, it is understood that when these two types of positive electrode active materials are used, the unit cell does not undergo any volume change in the actual use region of 0 to 200 mAh / g.

As a result of examining the volume expansion of the positive electrode active material during charge and discharge in such various oxide systems, we have found that when the positive electrode active material contains nickel and cobalt atoms in the same ratio, I found that the volume change was almost zero. Li _{1 ± x} Ni _1/3 Co _1/3 Mn
Even if elements other than nickel and cobalt are added, such as _1/3 O ₂ (x ≦ 0.1), the volume expansion is similarly zero. Therefore, what is important in the positive electrode active material in the present invention is that
That is, at least nickel atoms and cobalt atoms are included in the same ratio.

(3) Particle Size and Form FIGS. 7 and 8 show SEM photographs of the positive electrode active material particles. The positive electrode active material is powder.
It was found to be composed of (primary) crystal particles having a particle size of approximately 0.1 to 8 μm and secondary particles of crystal particles having a particle size of 2 to 30 μm. Similarly, Li ₄ T
As a result of observing the shape of the particles of i ₅ O ₁₂ by SEM, it was found that primary particles of approximately 0.6 μm or less aggregated to form secondary particles having an average grain size of approximately 1 μm. In the present invention, the material having the powder physical properties described above was used.

(4) Charging control The battery according to the present invention has an advantageous feature in terms of charging control when used for idling stop of an automobile. In the case of such an application, the battery is normally kept in a charged state of about 60% to 70% instead of a fully charged state. The reason for this is that regenerative charging is performed by braking the automobile, so that if the battery is in a fully charged state, it is likely to be overcharged and unsuitable. On the other hand, in the case of discharge, it is desirable to function as a constant pressure power source. Therefore, the charge / discharge voltage of the battery shows a flat potential of 2V up to about 60% of the capacity in the charge / discharge curve, and the voltage changes linearly according to the capacity in the charge side region. desirable. Since it is common and easy to control the charging by the voltage of the battery, the charging state of the battery can be accurately grasped by changing the voltage linearly in the region.

FIG. 9 shows a positive electrode using Li _{1 ± x} Ni _1/3 Co _1/3 Mn _1/3 O ₂ (x ≦ 0.1) and Li ₄ Ti ₅ O.
The charging / discharging curves b and a of the negative electrode using ₁₂ were shown. FIG. 10 shows the charge / discharge curve of the battery. Since the shape of the charge / discharge curve a of the negative electrode is completely flat in the entire region, the shape of the charge / discharge curve b of the positive electrode corresponds to the battery voltage as it is. As can be seen from the charge / discharge curve b in FIG. 9, the charge / discharge curve in the case of using the positive electrode shows a flat shape up to about 60% of the entire region,
It can be seen that the potential rises almost linearly when the charge is deeper than that. Li _{1 ± x} Ni
The same tendency is observed when _1/2 Co _1/2 O ₂ is used, although not as remarkable as when Li _{1 ± x} Ni _1/3 Co _1/3 Mn _1/3 O ₂ is used. .

From the above, it can be seen that the battery according to the present invention is an optimal battery system for applications in which charging is controlled as described above, such as for idling stop of automobiles. The combination of the positive electrode active material and the negative electrode active material in such an application has been found as a result of earnest research by the present inventors. Prior patents and prior art documents describing research from the same viewpoint are I can't find it.

(5) Capacity design of positive electrode and negative electrode When designing a capacity load of a battery, the capacity of either the positive electrode or the negative electrode is regulated. Such capacity regulation of the positive electrode or the negative electrode is intentionally designed from the application of the equipment used, the characteristics of the active material, and the like. In the 2V class battery system of the present invention, it is more preferable to regulate the capacity of the negative electrode. Specifically, the ratio of the negative electrode active material to the positive electrode active material is 0.5 or more and 1.
Less than 2. The reason for 1.2 is that the theoretical charge / discharge capacity per gram of the negative electrode exceeds the theoretical charge / discharge capacity of the positive electrode, so that this capacity difference is corrected. It can be said that it is a battery system.

The reason why the battery system regulated by the negative electrode is more preferable is as follows. The potential of the positive electrode is 4 V or more with respect to lithium. Since some positive electrodes have poor oxidation resistance depending on the electrolytic solution used, it is disadvantageous from the stability of the electrolytic solution to terminate charging by increasing the potential of the positive electrode. Also,
When lithium atoms are completely extracted from the positive electrode active material, it is expected that oxygen is gradually released, causing deterioration of the material and oxidation of the electrolyte, leading to deterioration of cycle life and battery characteristics.

(6) Current Collector for Positive Electrode and Negative Electrode In currently available lithium ion secondary batteries, aluminum is usually used as the current collector for the positive electrode, and copper is used as the current collector for the negative electrode. Considering the potential of each electrode, a metal material having excellent corrosion resistance is used. Patent Documents 6 and 7 relating to a technique using a lithium-containing titanium oxide as a negative electrode active material specify that aluminum and copper are used as current collectors for a positive electrode and a negative electrode, respectively.

In the present invention, it is preferable to use aluminum or an aluminum alloy as a current collector material for both the positive electrode and the negative electrode. The reason for this will be described below. First, by using aluminum with respect to copper, the battery can be reduced in weight, and at the same time, the cost can be reduced. In a battery system using graphite currently marketed as a negative electrode, the potential is as low as 0.2 V or less with respect to lithium metal, and it was impossible to use aluminum as a current collector. This is because aluminum starts to react with lithium ions at a potential higher than the potential at which the graphite of the negative electrode is charged and discharged.

However, in the battery system of the present invention, since the charge / discharge potential of the negative electrode is as high as 1.5 V, it is possible to use aluminum that does not react unless the potential falls below that potential. Further, when copper is used, copper ions are eluted in the electrolyte when the potential of the negative electrode increases due to deep discharge or the like. This copper ion precipitates on the negative electrode prior to the lithium insertion reaction by recharging, and inhibits the lithium insertion reaction. As a result, lithium is deposited as a metal in the form of needle crystals on the negative electrode surface. This causes a decrease in battery safety and a decrease in cycle life. On the other hand, when aluminum is used, elution and reprecipitation of metal ions do not occur.

Moreover, when the battery charger is broken while the negative electrode rate-determining battery is connected to the charger, the battery is overcharged, and excess lithium is supplied to the negative electrode. At this time, if the current collector of the negative electrode is copper, excess lithium metal will be deposited on the negative electrode as needle crystals. Such needle-like crystal lithium metal reduces the overcharge safety of the battery. However, aluminum has an ability to occlude lithium sufficiently. Therefore, when aluminum is used for the current collector of the negative electrode, lithium metal does not deposit on the negative electrode during overcharge, and the current collector can occlude lithium. This causes the current collector to play a role of a kind of safety mechanism, and as a result, does not reduce the overcharge safety of the battery.

(7) Separator In a battery using a general LiCoO ₂ / carbon material combination, a porous film composed mostly of polyethylene or propylene is used as a separator. This separator is considerably expensive because it is formed by melt-extrusion of a polymer material and stretching it in a biaxial direction to form a thin porous film. The main reason for requiring this film is considered as follows. In the battery, since graphite is used for the negative electrode, the potential of the battery is lowered to a position near the potential at which lithium metal is deposited. For this reason, various inconveniences occur. In some cases, lithium is slightly deposited on a part of the graphite surface by rapid charging or charging at a low temperature. Cobalt and impurity metals may elute due to excessive floating charge, etc., and may be deposited on the negative electrode, causing internal short circuit. For the purpose of suppressing such a phenomenon as much as possible, an olefin-based microporous membrane having strength and a small pore diameter is used.

Moreover, in order to ensure the safety at the time of the overcharge which assumed the failure of the charger etc., the separator is provided with the shutdown function which suppresses the raise of the battery temperature at the time of an overcharge. The shutdown function refers to a function of stopping the current flowing between the electrodes by contracting and crushing the fine pores of the separator at a certain temperature (about 135 ° C.).
In view of the above, an expensive porous film has been used as a separator in a battery using a conventional LiCoO ₂ / carbon material combination. However, since the separator has a small hole diameter, the separator becomes resistant to the movement of ions, and the high rate characteristic is sacrificed.

On the other hand, in the battery system of the present invention, since the potential of the negative electrode is 1.55 V and the potential at which lithium is deposited, there is almost no problem as described above. When aluminum is used as the current collector of the negative electrode, lithium is occluded, so that the problem of metal deposition does not occur in the case of overcharging. That is, a highly accurate shutdown function that a porous film has is not required. For these reasons, in the battery according to the present invention, it is possible to use a material having a large pore diameter such as a nonwoven fabric by preferably using aluminum or an aluminum alloy for the current collector of the negative electrode. Since the nonwoven fabric has a relatively large pore diameter and a large amount of liquid retention, it becomes possible to dramatically improve the rate characteristics, particularly the pulse characteristics, of the obtained battery. In addition, since a sophisticated and complicated manufacturing process such as a porous film is not required, the choice of separators is widened and inexpensive. It is preferable to use a nonwoven fabric having an average pore size of 0.1 μm or more.

In consideration of application to the battery according to the present invention, the material constituting the separator is preferably polyethylene, polypropylene, polybutylene terephthalate, or a mixture thereof. Polyethylene and polypropylene are stable to the electrolyte. When strength at high temperature is required, polybutylene terephthalate or the like is preferably used. The diameter of the fibers of these materials constituting the nonwoven fabric is preferably about 1 to 3 μm, and those in which the fibers are partially fused by a heated calender roll treatment are effective in reducing the thickness and improving the strength. It is.

(8) Nonaqueous Electrolyte A preferable electrolyte in the 2V class nonaqueous electrolyte secondary battery according to the present invention will be described.
The organic solvent used for the electrolyte has a potential window. The potential window is a measure of oxidation resistance and reducibility, and the wider the potential window, the more stable the organic solvent. General LiCoO ₂ /
In a non-aqueous secondary battery using a combination of carbon materials, the charge / discharge potential of cobalt is 4.5.
Oxidation resistance to near V and reduction resistance to near 0 V, which is the charge / discharge potential of graphite, are required. Note that the potential is based on lithium metal (the same applies hereinafter).

Therefore, organic solvents that cannot satisfy these potential windows have been excluded from the selection. In particular, it has been difficult to use a lactone organic solvent due to a problem relating to reduction resistance when graphite is used for the negative electrode. Propylene carbonate has also been difficult to use because it is simultaneously decomposed during charging and discharging of graphite. Since these solvents are inexpensive and have a large dielectric constant, they have the ability to sufficiently dissolve electrolytes (solutes and salts), and are useful solvents excellent in oxidation resistance. For similar reasons, it is also difficult to use trimethyl phosphate and triethyl phosphate. These solvents have a fire extinguishing action and are excellent in safety.

In the battery according to the present invention, it is possible to use all the solvents having these useful characteristics by using the materials as described above. In the present invention, Li ₄ Ti ₅ O ₁₂ (Li [Li _1/3 Ti _5/3 ] O ₄ ) is used for the negative electrode instead of graphite. From this, the potential on the negative electrode side rises to 1.55 V, and the reduction resistance required for the solvent is drastically reduced. Also,
A solvent such as propylene carbonate that is decomposed on the negative electrode surface by charge / discharge characteristic of graphite can also be used as an extremely effective solvent in the present invention.

On the other hand, the potential of the positive electrode rises to 4.7 V or higher, but since the oxidation resistance of these solvents is 5 V or higher, there is no problem in its use. In addition, sulfolane, methyl diglyme, fluorinated ethylene carbonate and the like excellent in oxidation resistance are also considered to be suitable solvents for the battery according to the present invention. In addition, DEC (dimethyl carbonate), MEC (
Solvents such as methyl ethyl carbonate and DMC (dimethyl carbonate) can also be used as diluents for highly viscous solvents.

In particular, ethylene carbonate (EC) is not necessarily required in the present invention, but EC is useful in view of liquid stability in a solvent having a large dielectric constant. Thus, oxidation resistance can be improved by fluorinating EC hydrogen. Fluorination is thought to be useful for the suppression of CO ₂ gas, which seems to be due to EC decomposition on the positive electrode during high-temperature storage of the battery, but this fluorinated EC is reductively decomposed when a carbon material is used for the negative electrode. It was difficult to use. However, these useful solvents can be used in the present invention. That is, by not using graphite, the selection range of the electrolytic solution can be dramatically expanded.
Note that the solute is not particularly limited, and LiPF ₆ and Li which have been conventionally used
In addition to BF ₄ , lithium salts of organic anions can also be used.

In conventional batteries, the carbon material is used for the negative electrode as well, so if it can be used alone, it is limited to select a very useful ionic liquid, or an ionic liquid is used. It was difficult to do. The present inventors specifically examined the possibility of using these ionic liquids. Use of ionic liquid alone is preferable from the viewpoint of safety, etc., but there are some that are highly viscous and some are solid as they are, and when considering manufacturing batteries using conventional production equipment Etc. may be used by mixing with the above-mentioned solvent. Even when mixed and used, the superiority can be secured to some extent.

Examples of the ionic liquid include the following. Cationic species include 1,2- and tri-substituted imidazolium, pyridinium, phosphonium, ammonium, pyrrolidinium, guanidinium, and isouronium. In addition, as anion species, halogen, sulfate, amide, imide, methane species, borate, phosphate,
Examples include antimonate, decanate, and cobalt tetracarbonyl. The structure of the cation species is shown in FIGS. 11 and 12, and the structure of the anion species is shown in FIG.

In the present invention, in particular, an ionic liquid based on a combination of trimethylpropylammonium cation and trifluoromethylsulfonylimide anion and an ionic liquid based on a combination of 1-ethyl-3-methylimidazolium cation and trifluoromethylimide anion are described in detail. It was examined. In particular, the latter imidazolium system undergoes reductive decomposition near 1 V, and is extremely difficult to use when a carbon material is used. Furthermore, even when these ionic liquids and a conventional non-aqueous electrolyte using ethylene carbonate or the like were mixed and used, it was confirmed that the obtained battery operated similarly and had an advantage.

(9) Other constituent members Other constituent materials that can be used when producing the nonaqueous electrolyte secondary battery according to the present invention will be described.
The conductive agent in the positive electrode mixture used for producing the positive electrode in the present invention is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the constituted battery. For example, graphite such as natural graphite (flaky graphite, etc.) and artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and conductive such as carbon fiber and metal fiber Organic fibers such as conductive fibers, metal powders such as carbon fluoride, copper, nickel, aluminum and silver, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and polyphenylene derivatives Examples thereof include conductive materials. These may be used alone or in any mixture as long as the effects of the present invention are not impaired.
Among these, artificial graphite, acetylene black, and nickel powder are particularly preferable. The addition amount of the conductive agent is not particularly limited, but is preferably 1 to 50% by weight of the positive electrode mixture, and particularly 1 to
30% by weight is preferred. In the case of carbon or graphite, 2 to 15% by weight is particularly preferable.

A preferable binder in the positive electrode mixture in the present invention is a polymer having a decomposition temperature of 300 ° C. or higher. For example, polyethylene, polypropylene, polytetrafluoroethylene (PTFE
), Polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP)
, Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA),
Vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer (ETFE resin), polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-penta Fluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, and vinylidene fluoride-perfluoromethyl A vinyl ether-tetrafluoroethylene copolymer etc. can be mentioned.
These may be used alone or in any mixture as long as the effects of the present invention are not impaired. In particular, the most preferred among these is polyvinylidene fluoride (PVDF).
) And polytetrafluoroethylene (PTFE).

The current collector of the positive electrode is not particularly limited as long as it is an electronic conductor that does not cause a chemical change in the constructed battery. Examples of the material constituting the current collector include stainless steel, nickel,
In addition to aluminum, titanium, various alloys, carbon, and the like, composites in which carbon, nickel, titanium, or silver is treated on the surface of aluminum or stainless steel can also be used. In particular, as described above, aluminum or an aluminum alloy is preferable. The surface of these materials can also be oxidized. Moreover, you may give an unevenness | corrugation to the collector surface by surface treatment. The shape may be one used in the field of batteries, such as foil,
Examples include films, sheets, nets, punched materials, lath bodies, porous bodies, foams, fiber groups, and nonwoven fabrics. The thickness is not particularly limited, but a thickness of 1 to 500 μm is preferably used.

The conductive agent in the negative electrode mixture is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in the constituted battery, similarly to the conductive agent in the positive electrode mixture. As the binder for the negative electrode, in addition to the materials described as being usable for the positive electrode, rubber-based binders such as styrene butadiene rubber can also be used.
As the current collector for the negative electrode, it is particularly preferable to use aluminum or an aluminum alloy for the reasons described above. In addition, there is no particular limitation as long as it is an electronic conductor that does not cause a chemical change in the constructed battery. For example, in addition to stainless steel, nickel, copper, titanium and carbon, the surface of copper or stainless steel treated with carbon, nickel, titanium or silver, Al
-Cd alloy or the like is used. The surface of the current collector may be uneven by oxidizing or surface treating the surface of these materials. As in the case of the positive electrode, for example, a foil, a film, a sheet, a net, a punched one, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like are used. The thickness is not particularly limited, but a thickness of 1 to 500 μm is preferably used.

The positive electrode and the negative electrode in the present invention are introduced for the purpose of improving the adhesion, conductivity, cycle characteristics, and charge / discharge efficiency of the current collector and the mixture layer, in addition to the mixture layer containing the cathode active material or the anode material. It may have a protective layer or the like introduced for the purpose of mechanical protection or chemical protection of the undercoat layer or the mixture layer. The undercoat layer and the protective layer can contain a binder, conductive agent particles, non-conductive particles, and the like.

The non-aqueous electrolyte has been described as having a wide selection range as described above, but it is naturally possible to use or mix the following well-known electrolytes. The non-aqueous electrolyte is composed of a solvent and a lithium salt dissolved in the solvent. Preferred solvents are esters alone or mixed esters. Among them, cyclic carbonates, cyclic carboxylic acid esters,
Acyclic carbonates and aliphatic carboxylic acid esters are preferred. Furthermore, a mixed solvent containing a cyclic carbonate and an acyclic carbonate, a mixed solvent containing a cyclic carboxylic acid ester,
A mixed solvent containing a cyclic carboxylic acid ester and a cyclic carbonate is preferred. Examples of the ester include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) and vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate ( EMC) and acyclic carbonates such as dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate (MF), methyl acetate (MA), methyl propionate (MP) and ethyl propionate (MA), γ- And cyclic carboxylic acid esters such as butyrolactone (GBL). Moreover, what contains aliphatic carboxylic acid ester is also preferable as needed. The aliphatic carboxylic acid ester is preferably contained in a range of 30% or less, more preferably 20% or less of the total solvent weight.

Examples of lithium salts that can be dissolved in these solvents include LiClO ₄ , LiBF ₄ , and LiP.
F ₆ , LiAlCl ₄ , LiSbF ₆ , LiSCN, LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , L
i (CF ₃ SO ₂ ) ₂ , LiAsF ₆ , LiN (CF ₃ SO ₂ ) ₂ , LiB ₁₀ Cl ₁₀ , lower aliphatic lithium carboxylate, lithium chloroborane, lithium tetraphenylborate, LiN (C
_{F 3 SO 2) (C 2} F 5 SO 2), LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, LiN
Examples include imides such as (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ). These can be used alone or in any combination within the range not impairing the effects of the present invention, for example, in the electrolytic solution to be used. Among them, it is particularly preferable to add LiPF _6.
The amount of the electrolytic solution added to the battery is not particularly limited, but a necessary amount may be used depending on the amount of the positive electrode active material and the negative electrode material and the size of the battery. The amount of lithium salt dissolved in a non-aqueous solvent is
Although not particularly limited, 0.2 to 2 mol / liter is preferable.

Moreover, the following solid electrolyte can also be used even if the electrolyte is not liquid. The solid electrolyte is classified into an inorganic solid electrolyte and an organic solid electrolyte. For inorganic solid electrolytes, Li
Nitrides, halides, oxyacid salts, and the like are well known. Among them, 80Li ₂ S-2
0P ₂ O ₅ , Li ₃ PO ₄ -63Li ₂ S-36SiS ₂ , 44LiI-3 as an amorphous substance
Sulfides such as 8Li ₂ S-18P ₂ S ₅ , oxides of Li _2.9 PO _3.3 N _0.46 and sulfides of Li _3.25 Ge _0.25 P _0.75 S ₄ , La _0.56 Li _0.33 TiO ₃ , Li _1.4 Al _0.3 Ti
_1.6 (PO ₄ ) ₃ oxides are promising. Furthermore, a method of forming a solid electrolyte layer at the joint interface at the same time as sintering each material by using a mixed sintered material of LiF and LiBO ₂ is also promising. In the battery system of the present invention, since there is no volume expansion of the positive electrode and the negative electrode, it is expected that desorption of the interface due to expansion / contraction, which has been a problem when using a solid electrolyte, is drastically improved. it can.

In the organic solid electrolyte, for example, polyethylene oxide, polypropylene oxide,
Polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol,
Polymer materials such as polyvinylidene fluoride, polyhexafluoropropylene and the like, derivatives, mixtures and composites thereof are effective. Moreover, the gel electrolyte which made the organic solid electrolyte contain the said non-aqueous electrolyte can also be used. Examples of the organic solid electrolyte include polymer matrices such as polyethylene oxide, polypropylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene, and derivatives, mixtures, and composites thereof. The material is effective. In particular, a copolymer of vinylidene fluoride and hexafluoropropylene or a mixture of polyvinylidene fluoride and polyethylene oxide is preferable.

As the shape of the battery, any of a coin type, a button type, a sheet type, a cylindrical type, a flat type, a square type, etc. can be applied. When the shape of the battery is a coin type or a button type, the mixture of the positive electrode active material and the negative electrode material is mainly compressed into a pellet shape and used. The thickness and diameter of the pellet may be determined depending on the size of the battery. In addition, the wound body of the electrode in the present invention does not necessarily have a true cylindrical shape, and may have a prismatic shape such as a long cylindrical shape or a rectangular shape whose cross section is an ellipse.

FIG. 16 is a side view showing a cross-section of a part of a cylindrical battery which is an embodiment of the nonaqueous electrolyte secondary battery according to the present invention. In the cylindrical battery shown in FIG. 16, an electrode plate group 4 obtained by winding a positive electrode and a negative electrode in a spiral shape through a separator is housed in a battery case 1. A positive electrode lead 5 is drawn from the positive electrode and connected to the sealing plate 2, and a negative electrode lead 6 is drawn from the negative electrode and connected to the bottom of the battery case 1. For the battery case and the lead plate, a metal or alloy having an organic electrolyte resistance and an electron conductivity can be used. For example,
A metal such as iron, nickel, titanium, chromium, molybdenum, copper, aluminum, or an alloy thereof is used. In particular, the battery case is preferably made of a stainless steel plate or an Al—Mn alloy plate, and the positive electrode lead is preferably aluminum. The negative electrode lead is preferably nickel or aluminum. In addition, various engineering plastics and a combination of these and a metal can be used for the battery case in order to reduce the weight.

Insulating rings 7 are respectively provided on the upper and lower portions of the electrode plate group 4. And electrolyte solution is inject | poured and a battery case is sealed using a sealing board. At this time, a safety valve can be provided on the sealing plate. In addition to the safety valve, various conventionally known safety elements may be provided. For example,
As the overcurrent prevention element, a fuse, a bimetal, a PTC element or the like is used. In addition to the safety valve, as a countermeasure against an increase in the internal pressure of the battery case, a method of cutting the battery case, a method of cracking the gasket, a method of cracking the sealing plate, or a method of cutting the lead plate can be used. Further, the charger may be provided with a protection circuit incorporating measures against overcharge and overdischarge, or may be connected independently. As a method for welding the cap, the battery case, the sheet, and the lead plate, a known method (for example, direct current or alternating current electric welding, laser welding, or ultrasonic welding) can be used. As the sealing agent for sealing, conventionally known compounds and mixtures such as asphalt can be used.

Hereinafter, the present invention will be described by way of representative examples, but the present invention is not limited thereto.
Example 1
First, two types of positive electrode active materials were produced under the following conditions. [Ni _1/2 Co ₁ obtained by coprecipitation method
_{/ 2} ] (OH) ₂ or [Ni _1/3 Mn _1/3 Co _1/3 ] (OH) ₂ was thoroughly mixed with LiOH.H ₂ O, and then the mixture was formed into pellets and fired. Li _{1 ± x} N at a firing temperature of 900 ° C.
i _1/2 Co _1/2 O ₂ (x ≦ 0.1) was obtained, the firing temperature was set to 1000 ° C., and Li _{1 ± x} Ni _1/3 Co
_1/3 Mn _1/3 O ₂ (x ≦ 0.1) was obtained.
Next, a single cell for electrochemical measurement was produced as follows. 80 parts by weight of the positive electrode active material, 10 parts by weight of acetylene black as a conductive agent, and 10 parts by weight of PVdF (polyvinylidene fluoride) as a binder are mixed and diluted with NMP (N-methyl-2-pyrrolidone). Then, the obtained mixture was applied on a current collector made of aluminum foil. The current collector after application was dried in vacuum at 60 ° C. for 30 minutes, and then cut into 15 × 20 mm ² . Further, the current collector after cutting was dried in a vacuum at 150 ° C. for 14 hours to obtain an electrode. The thickness of the electrode is 120μm ~ 190μ
between m.
The separator is a polyethylene porous film, and the electrolyte is EC.
A solution obtained by dissolving LiPF ₆ at 1.0 M in a solvent in which (ethylene carbonate) and DMC (dimethyl carbonate) were mixed at a volume ratio of 3 to 7 was used. The charging / discharging of the obtained single cell was repeated between predetermined voltage regions at a current density of 0.17 mA / cm ² .

A positive electrode of a battery using Li _{1 ± x} Ni _1/2 Co _1/2 O ₂ (x ≦ 0.1 ) as a positive electrode active material and Li ₄ Ti ₅ O ₁₂ having a spinel structure as a negative electrode active material FIG. 14 shows the measurement results of the total thickness of the negative electrode (total electrode thickness) using a high-precision extensometer (dilate meter). As the charge / discharge changes, the thickness changes so as to wave, and it can be confirmed that the measurement can be performed with high accuracy. Furthermore, as can be seen from FIG. 14, the total thickness change of the electrode is about 0.1 μm, which is about 0.5 μm even if the initial change is taken into account. Considering that the total electrode thickness immediately after fabrication is about 300 μm, it can be said that the substantial expansion and contraction of the electrode is zero. From this, it was proved that a volume change of zero can be realized as a battery by combining a positive electrode and a negative electrode having no volume change as described above. Even when Li _{1 ± x} Ni _1/3 Co _1/3 Mn _1/3 O ₂ (x ≦ 0.1) is used for the positive electrode, the change in thickness of the dilate meter shows a value equivalent to about 0.1 μm. (See FIG. 15).

Similarly, when the same measurement was performed using a negative electrode made of a carbon material, expansion of about 20% with respect to the thickness of the electrode was observed even with the initial change alone, and expansion / contraction of 10% or more was also caused by charge / discharge. Observed. In the battery system according to the present invention, this extremely small expansion / contraction caused by charging / discharging causes a long cycle life. In particular, the cycle life when charging / discharging at a high rate is dramatically improved as compared with the conventional battery system.

Example 2
In this example, a cylindrical battery shown in FIG. 16 was produced.
The battery case 1, the positive electrode lead 5, and the negative electrode lead 6 were made of nickel-plated iron, aluminum, and stainless steel, respectively.
The positive electrode (plate) was produced as follows. That is, the powdered positive electrode active material (Li _{1 ± x} Ni _1/2 Co _1/2 O ₂ (x ≦ 0.1) or Li _{1 ± x} Ni _1/3 Co _1/3 Mn _1/3 O ₂ ( x ≦ 0.1)) 8 parts by weight of carbon powder as a conductive agent and 5 parts by weight of polyvinylidene fluoride resin as a binder were mixed with 85 parts by weight. The obtained mixture was dispersed in dehydrated N-methylpyrrolidinone to obtain a slurry. This slurry was applied onto a positive electrode current collector made of aluminum foil, dried and rolled, and then the applied current collector was predetermined. The positive electrode was obtained by cutting into a size of.
Further, a negative electrode (plate) is except using Li ₄ Ti ₅ O ₁₂ having a spinel structure is a negative electrode active material in place of the positive electrode active material _{(Li [Li 1/3 Ti 5/3]} O 4) is It was produced in the same manner as the positive electrode.

In this invention, the nonwoven fabric made from a polypropylene was used as a separator. As the organic electrolytic solution, a solution obtained by dissolving 1.0 mol / liter of LiPF ₆ in a mixed solvent of ethylene carbonate (EC) and propylene carbonate (PC) in a volume ratio of 1: 1 was used. The dimensions of the produced cylindrical battery were 14.1 mm in diameter and 50.0 mm in height.

The cylindrical battery thus produced was charged at a constant voltage of 2.5 V and discharged at 100 mA.
The constant current was 1 V. The discharge capacity obtained at this time was 550 mAh. In this example, the battery was designed so that the battery capacities were approximately the same when the two positive electrode active materials were used. When charging the same battery again, constant voltage charging was performed between 1.9V and 2.35V. The capacity charged at this time is shown in Table 1.

From Table 1, according to the charge-discharge curves b shown in FIG. _{9, Li 1 ± x Ni 1/3} Co 1/3 Mn 1/3 in case of using the O ₂ voltage in the region above the 2.2V width have reduced the rate of increase capacity for, the increase rate of the capacitance versus voltage width reduced in more areas 2.0V in case of using _{Li 1 ± x Ni 1/2 Co 1/2} O 2 You can see that This indicates that the accuracy of voltage control with respect to the capacitance is increased in the voltage region.

Example 3
In this example, the preferred positive electrode and negative electrode capacity designs in the present invention were studied. A cylindrical battery was produced in the same manner as in Example 2 except that the weight ratio of the positive electrode active material amount per unit area of the positive electrode plate and the negative electrode active material amount per unit area of the negative electrode plate was variously changed. The cycle life was measured. The results are shown in Table 2. Cylindrical batteries with a weight ratio of 0.3, 1.2 and 1.5 are comparative examples. Regarding the charge / discharge cycle conditions, charging was performed at a constant current of 2.5 V and a maximum current of 1 C. The charging termination condition was a time cut of 2 hours from the start of charging. On the other hand, the discharge was performed at a constant current of 2 C and the cut was 1.0 V. Table 2 shows the number of cycles when the retention capacity was reduced to 98% of the initial capacity.

From Table 2, it can be seen that the cycle life decreases when the weight ratio is 1.2 or more. Therefore, it is preferable to design the battery so that the balance between the positive electrode and the negative electrode is substantially negative electrode rate limiting (negative electrode capacity regulation). However, if the positive electrode active material is increased more than necessary, the battery capacity is lowered, so that it is preferably substantially 0.5 or more and less than 1.2.

Example 4
In this example, the current collectors of the positive electrode and the negative electrode were examined.
A cylindrical battery was produced in the same manner as in Example 2 except that the positive and negative electrode current collectors were made of the materials shown in Table 3, and an overcharge test was performed. Table 3 shows the battery surface temperature during the overcharge test of each cylindrical battery. This battery surface temperature was the maximum battery temperature during overcharge. The current value was 1.5 C and constant current overcharge was performed.

From Table 3, it can be seen that heat generation of the battery during overcharge can be suppressed by using a current collector made of aluminum. As described above, by using the current collector made of aluminum in the battery system of the present invention, a 2V-class battery can be manufactured, and a battery with lighter weight, lower cost, and higher safety can be obtained.

Example 5
In this example, a preferred electrolyte was studied.
A cylindrical battery was fabricated in the same manner as in Example 2 except that the solvent and solute having the composition shown in Table 4 were used. And the capacity | capacitance obtained with the battery using the conventional electrolyte solution system was set to 100, and the capacity | capacitance obtained with the battery which changed electrolyte solution variously was evaluated as an index | exponent. This index is shown in Table 4. In addition, for comparison, the results are shown in which a cylindrical battery was fabricated and evaluated in the same manner using lithium cobaltate as the positive electrode active material and a graphite material as the negative electrode active material.
The indication of EC / DEC (3/7) represents that the weight ratio is 3: 7 with a mixed solvent of EC and DEC. The capacity of the battery obtained using this electrolytic solution was set to 100 in each battery system.

From Table 4, it can be seen that the conventional battery system using graphite cannot obtain a satisfactory capacity, and the electrolyte system that could not be used can be used without problems in the battery according to the present invention. It can be seen that a high battery can be obtained. Also, a mixed solvent of these solvents, a combination of conventionally used solvent types, or the like can be used.

Example 6
In the present invention, a cylindrical battery was produced and evaluated in the same manner as in Example 2 except that the solvents and solutes shown in Table 5 were used. In particular, an ionic liquid (A) of trimethylpropylammonium cation (TMPA) and trifluoromethylsulfonylimide anion (TFSI) or an ionic liquid of 1-ethyl-3-methylimidazolium cation and trifluoromethylimide anion (B) The case of using was examined in detail. Furthermore, the operation and superiority of a battery using a mixture of these ionic liquids and a conventional non-aqueous electrolyte using ethylene carbonate or the like were also confirmed by the same evaluation. Further, in order to confirm the safety effect of the ionic liquid, a hot box test at 150 ° C. was performed on a cylindrical battery fully charged with 2.5 V. A hot box containing a fully charged battery was heated from 30 ° C. to 150 ° C. at a rate of 5 ° C./min, and held at 150 ° C. for 3 hours. The battery surface temperature at this time was measured. The electrical characteristics and the results of the hot box test are shown in Table 5.

Table 5 shows that an ionic liquid that could not be used at all can be used alone. Moreover, it can be seen that by using the ionic liquid, almost no abnormal battery heating is observed in the hot box test, and the safety can be drastically improved. Although many ionic liquids are illustrated in FIGS. 9 to 11, problems such as viscosity remain, but the usability is improved by mixing with conventional solvents, in particular, mixing with EC, to improve safety and reliability. The effect can be expected.

Example 7
In this example, the preferred separator was examined.
A cylindrical battery was produced and evaluated in the same manner as in Example 2 except that the material shown in Table 6 was used for the separator (thickness 25 μm). Table 6 shows the pulse discharge characteristics and the maximum value of the battery surface temperature during overcharge. The pulse discharge was performed using a simple pulse of 1A, 5 seconds on, and 5 seconds off. When the pulse discharge time obtained when a conventional PE porous film was used was 100, other separators were used. The pulse discharge time of the battery was shown as an index. The overcharge was a constant current overcharge of 1.5C.

From Table 6, it can be seen that by using a nonwoven fabric in this battery system, the pulse discharge time can be greatly improved while keeping the safety of overcharge substantially constant. Moreover, it turns out that the fall of the voltage by a pulse current can be improved by using a nonwoven fabric.

As described above, if the battery system of the present invention, it is possible to dramatically improve the suppression of deterioration of life by the body Seki膨 Zhang has been a problem conventionally, the high-rate discharge characteristics, pulse characteristics, and the charge control . Therefore, the non-aqueous electrolyte secondary battery according to the present invention is characterized by a large-sized battery such as an electric power tool, a power source for a hybrid vehicle, a power source for an electric vehicle, etc., which are highly demanded for charge / discharge at a high rate and a cycle life. It can be demonstrated. The non-aqueous electrolyte secondary battery according to the present invention, other lead-acid battery alternative, can also be used as a battery for portable equipment.

DESCRIPTION OF SYMBOLS 1 Battery case 2 Sealing plate 3 Insulation packing 4 Electrode plate group 5 Positive electrode lead 6 Negative electrode lead 7 Insulation ring

Claims (9)

A positive electrode including a positive electrode active material having a layer structure, a negative electrode including a titanium oxide having a spinel structure as a negative electrode active material, and a non-aqueous electrolyte,
The positive electrode active materials are Li ₁ ± _x Ni _1/2 Co _1/2 O ₂ (x ≦ 0.1) and Li ₁ ± _x Ni _1/3 Co _1/3 Mn _1/3 O ₂ (x ≦ 0). 1) at least one of
The titanium oxide is Li ₄ Ti ₅ O ₁₂ ;
The positive electrode and the negative electrode each include a current collector made of aluminum or an aluminum alloy,
A non-aqueous electrolyte secondary battery in which the ratio of the weight of the negative electrode active material to the weight of the positive electrode active material is 0.5 or more and less than 1.2,
A charging / discharging method of a nonaqueous electrolyte secondary battery, wherein charging / discharging is performed so that a utilization rate of the positive electrode active material is 60% or less.   The non-aqueous electrolyte is selected from the group consisting of ethylene carbonate, propylene carbonate, γ butyl lactone, γ valerolactone, methyl diglyme, sulfolane, trimethyl phosphate, triethyl phosphate, methoxymethyl ethyl carbonate, and fluorinated ethylene carbonate. The charging / discharging method of the non-aqueous electrolyte secondary battery according to claim 1, comprising at least one kind.   The charging / discharging method of the non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte contains at least one ionic liquid.   The charge / discharge method of a nonaqueous electrolyte secondary battery according to claim 3, wherein the cation of the ionic liquid is selected from the group consisting of imidazolium, pyridinium, phosphonium, ammonium, pyrrolidinium, guanidinium, and isouronium.   The nonaqueous electrolyte according to claim 3 or 4, wherein the anion of the ionic liquid is selected from the group consisting of halogen, sulfate, sulfonate, amide, imide, methane, borate, phosphate, antimonate, decanate, and cobalt tetracarbonyl. Charge / discharge method of secondary battery.   The charging / discharging method of the nonaqueous electrolyte secondary battery in any one of Claims 1-5 which comprise the separator which consists of a nonwoven fabric.   The charge / discharge method of the nonaqueous electrolyte secondary battery according to claim 6, wherein the separator is composed of at least one selected from the group consisting of polyethylene, polypropylene, vinylon, nylon, polyethylene terephthalate, aramid resin, and polybutylene terephthalate. . The non-positive electrode according to any one of claims 1 to 7 , wherein the positive electrode active material comprises crystal particles having a particle size of 0.1 to 8 µm and secondary particles of the crystal particles having a particle size of 2 to 30 µm. A method for charging and discharging a water electrolyte secondary battery. The negative active material is composed of an average particle size of 10μm or less of secondary particles having an average particle size 0.6μm or less of primary particles formed by aggregation of claim 1-8 or the nonaqueous electrolyte secondary battery according to Charge and discharge method.