JP6851240B2 - Non-aqueous electrolyte secondary battery - Google Patents

Description

The present invention relates to a non-aqueous electrolyte secondary battery.

In recent years, environmentally friendly vehicles such as hybrid vehicles and electric vehicles have become widespread in earnest. At the same time, idling stop systems aimed at improving fuel efficiency at low cost and efficiently are also widely used, and there is an increasing need for low-cost batteries that can support the electrification of vehicles and the enhancement of power assist functions.

Batteries using lithium-titanium composite oxide as a negative electrode active material are known as batteries for realizing electric vehicle electrical equipment and strengthening of power assist function at low cost. For example, Patent Document 1 comprises a positive electrode having a positive electrode active material made of a lithium composite metal oxide having ^{a BET specific surface area of 2} to 30 m 2 / g, and lithium titanate represented by _{the formula Li 4 + a} Ti ₅ O _12. When a non-aqueous electrolyte secondary battery having a negative electrode having a negative electrode active material is charged at a higher current rate (high rate) than a non-aqueous electrolyte secondary battery using a negative electrode having a negative electrode active material made of graphite. It is disclosed that the charging characteristics of the battery are excellent and that the battery can be charged quickly.

Japanese Unexamined Patent Publication No. 2011-181367

A non-aqueous electrolyte secondary battery including a positive electrode containing a lithium composite metal oxide as a positive electrode active material and a negative electrode containing a lithium titanium composite oxide as a negative electrode active material, which is excellent in durability while improving high rate characteristics. A water electrolyte secondary battery is required.

An object of the present disclosure is to provide a non-aqueous electrolyte secondary battery having excellent durability while improving high rate characteristics.

The non-aqueous electrolyte secondary battery according to one aspect of the present disclosure is a combination of a positive electrode having a positive electrode mixture layer containing a first positive electrode active material and a second positive electrode active material and a negative electrode combination containing a lithium titanium composite oxide as a negative electrode active material. The first positive electrode active material comprises a negative electrode having an agent layer and a non-aqueous electrolyte, and the volume per mass of pores having a pore diameter of 100 nm or less is 8 mm ³ / g or more, and the second positive electrode active material is active. The volume of the pores having a pore diameter of 100 nm or less is 5 mm ³ / g or less, and the volume per mass of the pores having a pore diameter of 100 nm or less in the first positive electrode active material is the second. The pore diameter of the positive electrode active material is 100 nm or less, which is four times or more the volume per mass of the pores, and the content of the first positive electrode active material is the total amount of the first positive electrode active material and the second positive electrode active material. The amount of the non-aqueous electrolyte retained by the positive electrode is 0.49 g / cm ³ or more per unit volume of the positive electrode mixture layer.

The non-aqueous electrolyte secondary battery of the present disclosure makes it possible to provide a non-aqueous electrolyte secondary battery having excellent durability while improving high rate characteristics.

It is a perspective view which shows the structure of the non-aqueous electrolyte secondary battery which is an example of embodiment. It is sectional drawing of the electrode body included in the non-aqueous electrolyte secondary battery.

The present inventor has specified the volume per mass of the positive electrode having a pore diameter of 100 nm or less in the non-aqueous electrolyte secondary battery including the negative electrode containing a lithium titanium composite oxide as the negative electrode active material. It has a positive electrode mixture layer containing a first positive electrode active material and a second positive electrode active material, and the content of the first positive electrode active material is 30% by mass or less with respect to the total amount of the first positive electrode active material and the second positive electrode active material. When the retention amount of the non-aqueous electrolyte held by the positive electrode is 0.49 g / cm ³ or more per unit volume of the positive electrode mixture layer, the non-aqueous electrolyte is excellent in durability while improving the high rate characteristics. We have found that it will be possible to provide secondary batteries.

Hereinafter, an example of the embodiment of the present disclosure will be described in detail with reference to the drawings. The non-aqueous electrolyte secondary battery of the present disclosure is not limited to the embodiments described below. In addition, the drawings referred to in the description of the embodiment are schematically described, and the dimensions and the like of each component should be determined in consideration of the following description.

[Non-aqueous electrolyte secondary battery]
The configuration of the non-aqueous electrolyte secondary battery 10 will be described with reference to FIG. FIG. 1 is a perspective view showing a configuration of a non-aqueous electrolyte secondary battery 10 (hereinafter, also referred to as “battery 10”) which is an example of the present embodiment. The battery 10 includes, for example, an outer can 24 having a bottom and an opening, and a sealing plate 22 that closes the opening. The outer can 24 is a flat plate-shaped container having a substantially rectangular parallelepiped shape. In the outer can 24, for example, an electrode body 26 including a positive electrode 12, a negative electrode 14, and a separator 16 is housed together with a non-aqueous electrolyte (not shown). The electrode body 26 is housed in the outer can 24, for example, in a state of being covered with a resin insulating sheet.

The outer can 24 has a bottom portion 28, and an opening is provided at a position facing the bottom portion 28. The sealing plate 22 is a lid that closes the opening of the outer can 24, and the sealing plate 22 is provided with, for example, a positive electrode terminal 18, a negative electrode terminal 20, a liquid injection port 30, and a gas discharge valve 32. The positive electrode terminal 18 has a function of electrically connecting an external element and the positive electrode 12, and is attached in a state of being electrically insulated from the sealing plate 22 by an insulating gasket. The negative electrode terminal 20 has a function of electrically connecting an external element and the negative electrode 14, and is attached in a state of being electrically insulated from the sealing plate 22 by an insulating gasket. The liquid injection port 30 is for injecting a non-aqueous electrolyte, and the gas discharge valve 32 is for discharging the gas inside the battery to the outside of the battery.

FIG. 2 is a cross-sectional view of the electrode body 26 included in the battery 10. As shown in FIG. 2, the electrode body 26 has, for example, a winding structure in which a positive electrode 12 and a negative electrode 14 are wound via a separator 16, and is press-molded from a direction orthogonal to the central axis of the winding structure. It has a structure made up of.

The positive electrode 12 is composed of, for example, a positive electrode core and positive electrode mixture layers formed on both surfaces of the positive electrode core. The positive electrode mixture layer is formed, for example, so that an exposed portion of the positive electrode core body in which the positive electrode core body is exposed in a band shape is formed along the longitudinal direction at at least one end portion in the width direction. The negative electrode 14 includes, for example, a negative electrode core body and a negative electrode mixture layer formed on both surfaces of the negative electrode core body. The negative electrode mixture layer is formed, for example, so that an exposed negative electrode core body in which the negative electrode core body is exposed in a band shape is formed along the longitudinal direction at at least one end portion in the width direction. The positive electrode core body exposed portion is electrically connected to the positive electrode terminal 18, and the negative electrode core body exposed portion is electrically connected to the negative electrode terminal 20.

Next, the positive electrode 12, the negative electrode 14, the separator 16, the non-aqueous electrolyte, and the like included in the battery 10 will be described.

[Positive electrode]
As described above, the positive electrode 12 is composed of a positive electrode core such as a metal foil and a positive electrode mixture layer formed on the positive electrode core. For the positive electrode core, for example, a metal foil stable in the potential range of the positive electrode such as aluminum, a film in which the metal is arranged on the surface layer, or the like can be used. The positive electrode mixture layer contains, for example, a positive electrode active material, a conductive material and a binder.

The positive electrode mixture layer contains a first positive electrode active material and a second positive electrode active material as the positive electrode active material. In the first positive electrode active material, the volume per mass of pores having a pore diameter of 100 nm or less (hereinafter, _{also referred to as “pore volume V 100N} ”) is 8 mm ³ / g or more, and the fineness in the second positive electrode active material. The hole volume V _100N is 5 mm ³ / g or less. Further, the ratio of the pore volume V _100N in the first positive electrode active material to the pore volume V _100N in the second positive electrode active material (hereinafter, also referred to as “1st / 2nd pore volume ratio”) is 4 times or more. is there. Further, the content of the first positive electrode active material with respect to the total amount of the first positive electrode active material and the second positive electrode active material is 30% by mass or less. _{The method for measuring the pore volume V 100N} in the positive electrode active material will be described later.

Both the first positive electrode active material and the second positive electrode active material are lithium-containing transition metal oxides. The lithium-containing transition metal oxide is an oxide of a metal containing at least lithium (Li) and a transition metal element. The lithium-containing transition metal oxide may contain an additive element other than lithium (Li) and the transition metal element.

The battery 10 includes a negative electrode 14 containing a lithium titanium composite oxide as a negative electrode active material. Since the lithium-titanium composite oxide has high charge / discharge efficiency, the lower limit of the dischargeable potential at the positive electrode 12 is lower than that in the case of using the negative electrode active material made of a conventional carbon material. Since the expansion and contraction of the positive electrode active material particles become larger when the charge / discharge is performed at a higher depth, the occurrence of cracks in the positive electrode active material particles is accelerated by repeating the charge / discharge cycle at a high depth. It is thought that the width of the crack will also increase. Due to this, in the battery 10 using the lithium titanium composite oxide as the negative electrode active material, the conduction path in the positive electrode active material layer becomes complicated as compared with the case where the negative electrode active material made of the conventional carbon material is used. It is considered that the internal resistance of the battery 10 increases. Since the positive electrode active material having a small pore volume is likely to be affected by expansion and contraction, the problem of increased resistance due to particle cracking is more serious.

On the other hand, the battery 10 contains _{the first positive electrode active material and the second positive electrode active material having the pore volume V 100N} specified as the positive electrode active material in a specific content ratio. When pores having a pore diameter of 100 nm or less are present in the positive electrode active material, the effective reaction area of the positive electrode active material is increased and the diffusion distance of Li ions in the solid is significantly reduced, so that the resistance is reduced. , The high rate characteristic of the battery 10 can be improved. Since the positive electrode 12 contains a _{first positive electrode active material having a pore volume V 100N} of 8 mm ³ / g or more and a second positive electrode active material having a pore volume V _100N of 5 mm ³ / g or less. It is considered that the charging reaction preferentially occurs in the first positive electrode active material, and as a result, the first positive electrode active material is in a highly oxidized state as compared with the second positive electrode active material, and the reaction activity is increased.

At this time, the non-aqueous electrolyte existing in the vicinity of the first positive electrode active material is oxidatively decomposed by coming into contact with the first positive electrode active material in a highly oxidized state. Then, the oxidative decomposition product of the non-aqueous electrolyte diffuses and adheres to the surrounding positive electrode active material, so that a film is formed on the surface of the positive electrode active material. This film suppresses the occurrence and expansion of cracks in the positive electrode active material particles due to repeated charge / discharge cycles, thereby suppressing an increase in the resistance of the positive electrode active material that occurs due to repeated charge / discharge cycles, and high-rate charging of the battery 10. It is considered that the durability against the discharge cycle can be improved.

On the other hand, _{when the positive electrode active material contains only the first positive electrode active material having a pore volume V 100N} of 8 mm ³ / g or more, the reaction tends to occur uniformly in the entire region of the positive electrode mixture layer, and the positive electrode mixture layer tends to occur uniformly. It is unlikely that the reaction will be biased toward only a part of the positive electrode active material. Therefore, when only the first positive electrode active material is contained as the positive electrode active material, there are very few positive electrode active materials in a highly oxidized state, so that oxidative decomposition of the non-aqueous electrolyte and film formation by the oxidative decomposition products hardly occur. As a result, it is considered that the generation and expansion of cracks in the positive electrode active material particles are not suppressed, and the durability of the battery 10 against the charge / discharge cycle is not improved. Even when the positive electrode 12 contains only the second positive electrode active material as the positive electrode active material, it is considered that the durability of the battery 10 against the charge / discharge cycle is not improved for the same reason as described above.

In the battery 10, the volume ratio of the 1st and 2nd pores of the 1st positive electrode active material and the 2nd positive electrode active material is 4 times or more. When the first / second pore volume ratio is less than 4 times, since the pore volume V _{100 N} of the first positive electrode active material and the pore volume V _{100 N} of the second positive electrode active material are close, the first positive electrode active It is considered that the charging reaction is less likely to occur preferentially in the substance, and the first positive electrode active material is less likely to be in a highly oxidized state.

In the battery 10, the content of the first positive electrode active material in the positive electrode mixture layer is 30% by mass or less, preferably 20% by mass or less, based on the total amount of the first positive electrode active material and the second positive electrode active material. If the content of the first positive electrode active material is too large, the positive electrode mixture slurry used for producing the positive electrode 12 may have an increase in viscosity and a decrease in dispersibility, such as agglomeration of particles in a patchy manner. As a result, it is considered that the amount of the positive electrode mixture slurry coated is partially increased and the quality of the rolled electrode plate is deteriorated.

The lower limit of the content of the first positive electrode active material with respect to the total amount of the first positive electrode active material and the second positive electrode active material is not particularly limited, but is preferably, for example, 3% by mass or more, and more preferably 5% by mass or more. When the content of the first positive electrode active material is within the above range, the positive electrode active material that preferentially reacts to be in a highly oxidized state is not unevenly distributed in the positive electrode mixture layer, and the film is formed by oxidative decomposition of the non-aqueous electrolyte. It is considered that the formation is promoted and a uniform film can be formed on the positive electrode mixture layer.

Further, in the battery 10, the holding amount of the non-aqueous electrolyte held by the positive electrode 12 is preferably ^{0.49 g / cm 3 or more per unit volume of the positive electrode mixture layer.} If the amount of the non-aqueous electrolyte retained by the positive electrode 12 is too small, the electrolyte solution around the positive electrode active material particles inside the positive electrode mixture layer is insufficient, and the reaction resistance increases due to the decrease in the diffusivity of Li in the solid. This is because the high rate characteristic is lowered. Further, if the holding amount of the non-aqueous electrolyte held by the positive electrode 12 is too small, when the charge / discharge cycle is repeated in the battery 10, the non-aqueous electrolyte is consumed by the oxidative decomposition reaction of the non-aqueous electrolyte, and the non-aqueous electrolyte is insufficient, resulting in poor durability. This is because it drops significantly.

Here, for example, the holding amount of the non-aqueous electrolyte held by the positive electrode 12 is the non-water held in the positive electrode 12 in a state of being impregnated in the positive electrode mixture layer among the non-aqueous electrolytes contained in the battery 10. It refers to the amount of electrolyte, which is expressed as the mass per unit volume of the positive electrode mixture layer. Hereinafter, the amount of non-aqueous electrolyte retained by the positive electrode 12 / negative electrode 14 is also referred to as the “electrolyte retention amount” of the positive electrode 12 / negative electrode 14.

The upper limit of the electrolytic solution holding amount of the positive electrode 12 is not particularly limited. According to the findings of the present inventor, for example, even if the amount of the electrolytic solution retained in the positive electrode 12 ^{exceeds 0.70 g / cm 3} per unit volume of the positive electrode mixture layer, the interface between the positive electrode active material and the electrolytic solution is in contact with each other. It is considered that the influence on the resistance of the non-aqueous electrolyte secondary battery 10, that is, the influence on the high rate characteristics and durability of the non-aqueous electrolyte secondary battery 10 is small. On the other hand, if the non-aqueous electrolyte secondary battery 10 having a large amount of electrolyte retained in the positive electrode 12 is repeatedly charged and discharged in a harsh environment such as a particularly high temperature, gas may be easily generated. Therefore, in consideration of reliability, the amount of the electrolytic solution retained in the positive electrode 12 ^{is preferably 0.70 g / cm 3} or less.

The positive electrode mixture layer of the positive electrode 12 contains, as positive electrode active materials, a first positive electrode active material having a pore volume V _100N of 8 mm ³ / g or more and a second positive electrode having a pore volume V _100N of 5 mm ³ / g or less. Includes at least active material. _{The upper limit of the pore volume V 100N} of the first positive electrode active material is not particularly limited, but is preferably, for example, 50 mm ³ / g or less, and more preferably 20 mm ³ / g or less. _{Regarding the pore volume V 100N} of the second positive electrode active material, the lower limit is not particularly limited, and is preferably 2 mm ³ / g or less.

_{For the pore volume V 100N} in the positive electrode active material, for example, a pore distribution curve is created by the BJH method based on the measurement result of the adsorption amount of nitrogen gas with respect to the pressure by the nitrogen adsorption method, and the pore diameter is 100 nm or less. It can be calculated by summing the volumes of the pores in the range. The BJH method is a method of determining the pore distribution by calculating the pore volume with respect to the pore diameter using a cylindrical pore as a model. The pore distribution based on the BJH method can be measured using, for example, a gas adsorption amount measuring device (manufactured by Kantachrome).

The first positive electrode active material and the second positive electrode active material are preferably layered lithium transition metal oxides having a layered crystal structure. For example, the general formula _{(1) Li 1 + x M} a O layered lithium transition metal oxide represented by _{2 + b} can be mentioned, in formula (1), x, a and b, x + a = 1, -0.2 ≦ The conditions of x ≦ 0.2 and −0.1 ≦ b ≦ 0.1 are satisfied, and M is selected from the group consisting of nickel (Ni), cobalt (Co), manganese (Mn) and aluminum (Al). It is a metallic element containing at least one element. Since the layered lithium transition metal oxide tends to be in a highly oxidized state when lithium ions are extracted during the charging reaction, the above-mentioned oxidative decomposition and film formation of the non-aqueous electrolyte are likely to occur, and the non-aqueous electrolyte secondary battery 10 The effect of improving durability against the charge / discharge cycle is remarkably exhibited. As the layered lithium transition metal oxide, lithium nickel cobalt manganate represented by the above general formula (1) and containing Ni, Co and Mn as M is particularly preferable.

The layered lithium transition metal oxide may contain other additive elements other than Ni, Co, Mn and Al, for example, an alkali metal element other than Li, a transition metal element other than Mn, Ni and Co, and alkaline soil. Examples thereof include metal group elements, Group 12 elements, Group 13 elements other than Al, and Group 14 elements. Specific examples of other additive elements include, for example, zirconium (Zr), boron (B), magnesium (Mg), titanium (Ti), iron (Fe), copper (Cu), zinc (Zn), and tin (Sn). ), Sodium (Na), Potassium (K), Barium (Ba), Strontium (Sr), Calcium (Ca), Tungsten (W), Molybdenum (Mo), Niob (Nb), Silicon (Si) and the like. ..

The composition of the positive electrode active material and the compound used as the negative electrode active material in the battery 10 can be measured using an ICP emission spectroscopic analyzer (for example, manufactured by Thermo Fisher Scientific, trade name "iCAP6300", etc.).

An example of a method for synthesizing a layered lithium transition metal oxide used as a first positive electrode active material and a second positive electrode active material will be described. For example, an oxide obtained by firing a lithium-containing compound such as lithium hydroxide and a hydroxide containing a metal element M other than lithium is mixed at a desired mixing ratio, and the mixture is fired. , Secondary particles formed by agglomeration of primary particles of layered lithium transition metal oxide represented by the above general formula (1) can be synthesized. The mixture is fired in the atmosphere or in an oxygen stream. The firing temperature is, for example, about 500 to 1100 ° C., and the firing time is, for example, about 1 to 30 hours when the firing temperature is 500 to 1100 ° C.

_{The pore volume V 100N} in the layered lithium transition metal oxide used as the first positive electrode active material and the second positive electrode active material can be adjusted, for example, when preparing the hydroxide containing the metal element M. The hydroxide containing the metal element M is obtained, for example, by dropping an alkaline aqueous solution such as sodium hydroxide into an aqueous solution containing the compound of the metal element M and stirring, and the temperature of the aqueous solution and the dropping time of the alkaline aqueous solution at this time. _{The pore volume V 100N} in the obtained layered lithium transition metal oxide can be adjusted by adjusting the stirring speed, pH, and the like.

The average particle size of the first positive electrode active material and the second positive electrode active material is not particularly limited, but is preferably 2 μm or more, and more preferably 3 μm or more, for example. When the average particle size of the first positive electrode active material and the second positive electrode active material is less than 2 μm, the conductive path by the conductive material in the positive electrode mixture layer may be obstructed and the cycle characteristics at high rates may be deteriorated. The upper limit of the average particle size of the first positive electrode active material and the second positive electrode active material is not particularly limited, but is preferably 30 μm or less, for example. If it exceeds 30 μm of the first positive electrode active material and the second positive electrode active material, the load characteristics may be deteriorated due to the decrease in the reaction area. When the first positive electrode active material and the second positive electrode active material are secondary particles formed by aggregating the primary particles, the average particle size of the secondary particles of the first positive electrode active material and the second positive electrode active material is 2 μm. It is preferably in the range of 30 μm or more.

The average particle size of the positive electrode active material and the negative electrode active material in the present disclosure is the volume average particle size measured by the laser diffraction method, and means the median diameter at which the volume integrated value is 50% in the particle size distribution. The average particle size of the positive electrode active material and the negative electrode active material can be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device (manufactured by HORIBA, Ltd.).

In the positive electrode 12 according to the present embodiment, for example, (1) the first positive electrode active material, the second positive electrode active material, the conductive material and the binder are mixed, and then N-methyl-2-pyrrolidone (NMP) or the like is dispersed. A slurry preparation step of adding a medium to prepare a positive electrode mixture slurry, (2) a slurry coating step of applying the positive electrode mixture slurry to the surface of the positive electrode core to form a coating layer, and (3) on the positive electrode core. If it is manufactured by a method having a drying step of drying the coating layer formed in the above to form a positive electrode mixture layer, and (4) a rolling step of rolling the positive electrode mixture layer using a rolling means such as a rolling roll. Good. The method of applying the slurry to the surface of the positive electrode core in the coating step is not particularly limited, and a well-known coating device such as a gravure coater, a slit coater, or a die coater may be used.

Examples of the conductive material contained in the positive electrode mixture layer include carbon materials such as carbon black, acetylene black, ketjen black, and graphite. These may be used alone or in combination of two or more types.

Examples of the binder contained in the positive electrode mixture layer include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimides, acrylic resins, and polyolefins. Further, these resins may be used in combination with carboxymethyl cellulose (CMC) or a salt thereof, polyethylene oxide (PEO) and the like. These may be used alone or in combination of two or more.

In the battery 10, as described above, the positive electrode 12 holds a specific range of non-aqueous electrolyte in the positive electrode mixture layer. Examples of the method for measuring the holding amount of the electrolytic solution of the positive electrode 12 include the following methods.

The battery 10 is discharged in an atmosphere of, for example, 25 ° C. with a discharge current of 1 C until the SOC (charging depth) becomes 0%. The discharge at this time may be performed until, for example, the voltage drops to 1.5 V, and when the negative electrode active material mainly contains a carbon-based material, the discharge may be performed until the voltage drops to 2.5 V. When the SOC becomes 0%, the battery 10 is disassembled, the electrode body 26 is taken out, and further separated into a positive electrode 12, a negative electrode 14, and a separator 16. A certain range is cut out from the separated positive electrode 12, and a sample having a positive electrode core and positive electrode mixture layers on both sides thereof is obtained. By immersing the obtained sample in an extraction solvent (for example, water) and shaking it, the non-aqueous electrolyte impregnated in the positive electrode mixture layer of the positive electrode 12 can be extracted into the extraction solvent. The above shaking may be performed using a known shaking device such as a shaking device (manufactured by AS ONE Corporation, trade name "SHAKER SRR-2").

Next, the concentration of the non-aqueous electrolyte in the extraction solvent is measured using a known analyzer such as, for example, an ICP emission spectroscopic analyzer (iCAP6300 manufactured by Thermo Fisher Scientific). As will be described later, the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent, and the ICP emission spectroscopic analyzer can quantify both the non-aqueous solvent and the electrolyte salt in the extraction solvent. The weight of the non-aqueous electrolyte (non-aqueous solvent and electrolyte salt) quantified as described above and the volume of the positive electrode mixture layer in the sample separately measured (or the weight of the positive electrode mixture layer in the sample and the positive electrode mixture). The non-aqueous electrolyte per unit volume of the positive electrode mixture layer can be calculated as the amount of the electrolytic solution retained by the positive electrode 12 based on the layer density).

The method for measuring the amount of electrolyte retained in the positive electrode 12 is not limited to the above. For example, the non-aqueous electrolyte contained in the extraction solvent after shaking can be quantified by a known analysis method such as ion chromatography or gas chromatography. Further, the amount of the non-aqueous electrolyte extracted from the sample may be specified from the amount of change in the weight of the extraction solvent before and after the extraction of the sample of the positive electrode 12.

The amount of the electrolytic solution retained in the positive electrode 12 can be adjusted, for example, by adjusting the density of the positive electrode mixture layer, and also by adjusting the conductive agent, the binder, the liquid absorbing agent, and the combination thereof used for the positive electrode 12. The density of the positive electrode mixture layer is, for example, the viscosity of the positive electrode mixture slurry, the contents of the positive electrode active material, the conductive material and the binder in the positive electrode mixture slurry, and the positive electrode mixture in the above method for producing the positive electrode 12. It can be adjusted by adjusting the coating amount of the slurry, the pressure at the time of rolling, and the like. The total weight of the first positive electrode active material and the second positive electrode active material in the positive electrode mixture layer is, for example, 80% by mass or more and 94.5% by mass or less. The compounding ratio of the conductive material in the positive electrode mixture layer is, for example, 5% by mass or more and 15% by mass or less. The compounding ratio of the binder in the positive electrode mixture layer is, for example, 0.5% by mass or more and 5% by mass or less.

[Negative electrode]
The negative electrode 14 is composed of a negative electrode core made of a metal foil or the like and a negative electrode mixture layer formed on the negative electrode core. As the negative electrode core, a metal foil stable in the potential range of the negative electrode such as aluminum, a film in which the metal is arranged on the surface layer, or the like can be used. The negative electrode mixture layer contains a negative electrode active material and a binder. The negative electrode 14 can be manufactured according to the above-mentioned manufacturing method of the positive electrode 12, and for example, a negative electrode mixture slurry containing a negative electrode active material, a binder, and the like is applied and dried on the negative electrode core to form a negative electrode mixture layer. Then, by rolling the negative electrode mixture layer with a rolling means such as a rolling roll, the negative electrode 14 having the negative electrode mixture layers formed on both sides of the negative electrode core can be manufactured.

The negative electrode active material used for the negative electrode 14 contains a lithium titanium composite oxide. The lithium-titanium composite oxide is represented by the general formula (2) Li _{4 + y} Ti ₅ O ₁₂ (in the general formula (2), y is 0 or more and 1 or less), and has a spinel-type crystal structure.

The negative electrode active material composed of the lithium-titanium composite oxide may be synthesized, for example, by a method similar to the method for synthesizing the layered lithium transition metal oxide. For example, a lithium-containing compound such as lithium hydroxide and a titanium-containing compound such as titanium dioxide and titanium hydroxide are mixed at a desired mixing ratio, and the mixture is fired to obtain the above general formula (2). Secondary particles formed by aggregating the primary particles of the represented lithium titanium composite oxide can be synthesized. The calcination of the mixture of the lithium-containing compound and the titanium-containing compound may be performed in the air (or in an oxygen stream), for example, the calcination temperature at that time is, for example, about 500 to 1100 ° C., and the calcination temperature is 500 to 1100. When the temperature is about ° C., the firing time is, for example, 1 to 30 hours.

As the negative electrode active material, in addition to the lithium titanium composite oxide, a compound capable of reversibly occluding and releasing lithium ions, for example, a carbon material such as natural graphite and artificial graphite, and a metal capable of alloying with lithium such as Si and Sn. Etc. may be contained.

As the binder used for the negative electrode 14, a known binder can be used, and as in the case of the positive electrode 12, a fluororesin such as PTFE, a PAN, a polyimide resin, an acrylic resin, and a polyolefin resin can be used. Etc. can be used. Examples of the binder used when preparing a negative electrode mixture slurry using an aqueous solvent include CMC or a salt thereof, styrene-butadiene rubber (SBR), polyacrylic acid (PAA) or a salt thereof, and polyvinyl. Alcohol (PVA) and the like can be mentioned.

In the non-aqueous electrolyte secondary battery 10 according to the present embodiment, the electrolyte holding amount of the negative electrode 14 is preferably ^{0.58 g / cm 3 or more per unit volume of the negative electrode mixture layer.} This is because when the electrolyte holding amount of the negative electrode 14 is within the above range, the high rate characteristics and durability of the non-aqueous electrolyte secondary battery 10 can be further improved.

The measurement of the electrolytic solution holding amount of the negative electrode 14 may be performed in the same manner as the method for measuring the electrolytic solution holding amount of the positive electrode 12 described above. Further, the adjustment of the electrolytic solution holding amount of the negative electrode 14 may be performed in the same manner as the above-described method of adjusting the electrolytic solution holding amount of the positive electrode 12.

[Non-aqueous electrolyte]
The non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent. As the non-aqueous solvent used for the non-aqueous electrolyte, for example, amides such as esters, ethers, nitriles and dimethylformamide, and a mixed solvent of two or more of these can be used, and these solvents can be used. A halogen substituent in which at least a part of hydrogen is replaced with a halogen atom such as fluorine can also be used.

Examples of the esters contained in the non-aqueous electrolyte include cyclic carbonates, chain carbonates, and carboxylic acid esters. Specifically, for example, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, vinylene carbonate; dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), methyl. Chain carbonates such as propyl carbonate, ethyl propyl carbonate and methyl isopropyl carbonate; chain carboxylic acid esters such as methyl propionate (MP), ethyl propionate, methyl acetate, ethyl acetate and propyl acetate; and γ-butyrolactone ( GBL), cyclic carboxylic acid esters such as γ-valerolactone (GVL) and the like can be mentioned. Cyclic carboxylic acid esters such as γ-butyrolactone (GBL) and γ-valerolactone (GVL) can be mentioned.

Examples of ethers contained in the non-aqueous electrolyte include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahexyl, propylene oxide, 1,2-butylene oxide, and 1,3-. Cyclic ethers such as dioxane, 1,4-dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineole, crown ether; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl Ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, o-dimethoxybenzene, 1,2-diethoxyethane, Chain ethers such as 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, 1,1-dimethoxymethane, 1,1-diethoxyethane, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl, etc. Can be mentioned.

Examples of nitriles contained in non-aqueous electrolytes include acetonitrile, propionitrile, butyronitrile, valeronitrile, n-heptanenitrile, succinonitrile, glutaronitrile, adiponitrile, pimeronitrile, 1,2,3-propanetricarbohydrate. Examples thereof include nitriles and 1,3,5-pentantricarbonitrile.

Examples of halogen substituents contained in non-aqueous electrolytes include fluorinated cyclic carbonates such as 4-fluoroethylene carbonate (FEC), fluorinated chain carbonates, and methyl 3,3,3-trifluoropropionate (FMP). ) And the like, fluorinated chain carboxylic acid ester and the like.

The electrolyte salt used for the non-aqueous electrolyte is preferably a lithium salt. _Examples of the lithium _{salt, LiBF 4, LiClO 4, LiPF} 6, LiAsF 6, LiSbF 6, LiAlCl 4, LiSCN, LiCF 3 SO 3, LiC (C 2 F 5 SO 2), LiCF 3 CO 2, Li (P (C ₂ O ₄ ) F ₄ ), Li (P (C ₂ O ₄ ) F ₂ ), LiPF _6-x (C _n F _{2n + 1} ) _x (1 ≦ x ≦ 6, n is 1 or 2), LiB ₁₀ Cl ₁₀ , LiCl, LiBr, LiI, lithium chloroborane, lithium lower aliphatic carboxylate, Li ₂ B ₄ O ₇ , Li (B (C ₂ O ₄ ) ₂ ) [lithium-bisoxalate volate (LiBOB)], Borates such as Li (B (C ₂ O ₄ ) F ₂ ), LiN (FSO ₂ ) ₂ , LiN (C ₁ F _{2l + 1} SO ₂ ) (C _m F _{2m + 1} SO ₂ ) {l, m is 1 or more Examples thereof include imide salts such as integer}. Only one type of lithium salt may be used, or two or more types may be mixed and used.

As described above, the non-aqueous electrolyte comes into contact with the first positive electrode active material in a highly oxidized state in the positive electrode mixture layer and is oxidatively decomposed to form a film of the oxidative decomposition product on the surface of the positive electrode active material. From this viewpoint, it is preferable to use _{LiPF 6} as the non-aqueous electrolyte.

[Separator]
For the separator 16, for example, a porous sheet having ion permeability and insulating property is used. Specific examples of the porous sheet include a microporous thin film, a woven fabric, and a non-woven fabric. As the material of the separator 16, olefin resins such as polyethylene and polypropylene, cellulose and the like are suitable. The separator 16 may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as an olefin resin. Further, it may be a multilayer separator containing a polyethylene layer and a polypropylene layer, and a resin such as an aramid resin or an inorganic fine particle such as alumina or titania coated on the surface of the separator 16 can also be used.

In the above description, the battery 10 has been described by the electrode body 26 having a wound structure. However, the configuration of the non-aqueous electrolyte secondary battery of the present disclosure is not limited to this configuration. For example, the positive electrode 12 and the negative electrode 14 may form a zigzag-folded electrode body with the band-shaped positive electrode 12 and the band-shaped negative electrode 14 facing each other. Further, a plurality of single-wafer-shaped positive electrode plates and a plurality of single-wafer-shaped negative electrode plates may be alternately laminated via a separator 16 to form a laminated electrode body. Further, the exterior body is not limited to the square exterior body. For example, a cylindrical metal outer body, a coin-shaped outer body may be used, or the electrode body may be covered with a laminated film. The material of the outer body does not need to be made of a conductive material as long as the outer body and the electrode body are not electrically connected to each other. For example, a resin outer body may be used.

<Example 1>
[Cathode preparation]
A lithium-containing compound and an oxide obtained by firing a hydroxide containing a metal element other than lithium including nickel (Ni), cobalt (Co), and manganese (Mn) are mixed at a desired mixing ratio. By mixing and firing the mixture, secondary particles formed by aggregating the primary particles of the layered lithium transition metal oxide are synthesized, and the layered lithium transition metal oxidation used as the first positive electrode active material and the second positive electrode active material. I got something.

According to the above method, a layered lithium transition metal oxide (first positive electrode active material) represented _{by the composition formula Li 1.054} Ni _0.199 Co _0.597 Mn _0.199 Zr _0.005 O _{2 and a composition formula.} A layered lithium transition metal oxide (second positive electrode active material) represented by Li _1.067 Ni _0.498 Co _0.199 Mn _0.299 Zr _0.005 O _{2 is mixed at a mass ratio of 3: 7.} A mixture was obtained. The composition of the positive electrode active material and the compound used as the negative electrode active material described later was measured using an ICP emission spectroscopic analyzer (manufactured by Thermo Fisher Scientific Co., Ltd., trade name "iCAP6300").

_{The pore volume V 100N} of the first positive electrode active material measured by the BJH method was 8 mm ³ / g, and the pore volume V _100N of the second positive electrode active material was 2 mm ³ / g. As a result of measuring the volume average particle diameters of the first positive electrode active material and the second positive electrode active material using a laser diffraction scattering type particle size distribution measuring device (manufactured by Horiba Seisakusho Co., Ltd.), the volume average particle diameter of the first positive electrode active material Was 5.0 μm, and the volume average particle size of the second positive electrode active material was 2.0 μm.

91: 7 of the positive electrode active material (mixture of the first positive electrode active material and the second positive electrode active material) produced by the above method, carbon black (conductive material), and polyvinylidene fluoride (PVDF) (binding agent). The mixture was mixed at a mass ratio of 2: 2. N-Methyl-2-pyrrolidone (NMP) was added to the mixture as a dispersion medium, and the mixture was stirred using a mixer (TK Hibismix manufactured by Primix Corporation) to prepare a positive mixture slurry. The viscosity (unit: mPa · s) of the prepared positive electrode mixture slurry was measured using a B-type viscometer (manufactured by Eiko Seiki Co., Ltd., product name “Brookfield viscometer”).

The slurry was applied onto an aluminum foil as a positive electrode core, and the coating film was dried to form a positive electrode mixture layer. Next, the positive electrode mixture layer was rolled by a rolling roll to prepare a positive electrode 12 having positive electrode mixture layers formed on both sides of the aluminum foil. The slurry was applied onto an aluminum foil as a positive electrode core, and the coating film was dried to form a positive electrode mixture layer. Next, the positive electrode mixture layer was rolled by a rolling roll to prepare a positive electrode 12 having positive electrode mixture layers formed on both sides of the aluminum foil. As a rolling method in the present embodiment, for example, the thickness of the positive electrode mixture layer before rolling is 110 to 115 μm, and the thickness of the positive electrode mixture layer after rolling is adjusted to be in the range of 70 to 90 μm. , The holding amount of the positive electrode mixture layer can be adjusted within the above range. The method of controlling the amount of the electrolytic solution retained in the positive electrode mixture layer used in the non-aqueous electrolyte secondary battery of the present disclosure is not limited to the above-mentioned rolling method.

[Preparation of negative electrode]
Lithium-titanium composite oxide represented by the composition formula Li ₄ Ti ₅ O ₁₂ , carbon black (conductive material), and polyvinylidene fluoride (PVDF) were mixed at a mass ratio of 90: 8: 2. NMP was added to the mixture, and the mixture was stirred using a mixer (TK Hibismix manufactured by Primix Corporation) to prepare a negative electrode mixture slurry. Next, the negative electrode mixture slurry is applied onto the aluminum foil which is the negative electrode core, the coating film is dried, and then the coating film is rolled by a rolling roll to form negative electrode mixture layers on both sides of the aluminum foil. Negative electrode 14 was produced.

[Preparation of non-aqueous electrolyte]
Propylene carbonate (PC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed at a volume ratio of 25:35:40 to prepare a mixed solvent. A non-aqueous electrolyte was prepared by dissolving _{LiPF 6 in the} mixed solvent to a concentration of 1.2 mol / L. The blending ratio of the negative electrode active material in the negative electrode mixture layer is, for example, 80% by mass or more and 95% by mass or less. The blending ratio of the conductive material in the negative electrode mixture layer is, for example, 5% by mass or more and 15% by mass or less. The compounding ratio of the binder in the negative electrode mixture layer is, for example, 1% by mass or more and 5% by mass or less.

[Battery production]
The positive electrode 12 and the negative electrode 14 obtained above were spirally wound through a separator 16 made of a microporous polypropylene film and then press-molded to prepare a flat electrode body 26. A current collector portion was welded to each of the positive electrode core body exposed portion and the negative electrode core body exposed portion formed at both ends in the width direction of the electrode body 26. Next, the electrode body 26 to which the current collector portion is welded is housed in an aluminum outer can 24, the above non-aqueous electrolyte is injected from the liquid injection port 30, and then the opening is sealed with a sealing plate 22. Therefore, a non-aqueous electrolyte secondary battery 10 having a rated capacity of 10 Ah shown in FIG. 1 was produced.

[Measurement of electrolyte retention]
As a result of discharging the battery 10 in an atmosphere of 25 ° C. with a discharge current of 1 C until the SOC (charging depth) becomes 0%, the voltage drops to 1.5 V. Next, the battery 10 was disassembled, the electrode body was taken out, and further separated into a positive electrode 12, a negative electrode 14, and a separator 16. A certain range was cut out from the obtained positive electrode 12, and a sample having a positive electrode core and positive electrode mixture layers on both sides thereof was obtained. The obtained sample is immersed in water (extraction solvent) and shaken using a shaking device (manufactured by AS ONE Co., Ltd., trade name "SHAKER SRR-2"), whereby the positive electrode 12 is held in the positive electrode mixture layer. An extract obtained by extracting the non-aqueous electrolyte into water was obtained. Next, the concentration of the non-aqueous electrolyte in the extract was quantified using an ICP emission spectroscopic analyzer (iCAP6300 manufactured by Thermo Fisher Scientific), and the weight of the non-aqueous electrolyte extracted from the sample of the positive electrode 12 was calculated. The amount of electrolyte retained in the positive electrode 12 was determined based on the calculated weight of the non-aqueous electrolyte and the volume of the positive electrode mixture layer in the sample separately measured. Similarly, the amount of the electrolytic solution retained in the negative electrode 14 was determined. As a result, in the battery 10 of Example 1, the electrolytic solution holding amount of the positive electrode 12 was 0.655 g / cm ³ , and the electrolytic solution holding amount of the negative electrode 14 was 0.628 g / cm ³ .

<Example 2>
In the production of the battery 10, the battery 10 having the same configuration as that of the first embodiment was produced except that the pressure for rolling the positive electrode mixture layer was adjusted and the pressure for rolling the negative electrode mixture layer was adjusted. In the battery 10 of Example 2, the electrolytic solution holding amount of the positive electrode 12 was 0.662 g / cm ³ , and the electrolytic solution holding amount of the negative electrode 14 was 0.618 g / cm ³ .

<Example 3>
In the production of the non-aqueous electrolyte secondary battery 10, the battery 10 having the same configuration as that of the first embodiment was produced except that the pressure for rolling the positive electrode mixture layer was adjusted. In the battery 10 of Example 3, the electrolytic solution holding amount of the positive electrode 12 was 0.490 g / cm ³ , and the electrolytic solution holding amount of the negative electrode 14 was 0.628 g / cm ³ .

<Comparative example 1>
A non-aqueous electrolyte secondary battery having the same configuration as in Example 1 except that the first positive electrode active material was not used as the positive electrode active material and only the second positive electrode active material was used in the process of producing the positive electrode. Made. In the non-aqueous electrolyte secondary battery of Comparative Example 1, the electrolyte holding amount of the positive electrode was 0.655 g / cm ³ , and the electrolyte holding amount of the negative electrode was 0.628 g / cm ³ .

<Comparative example 2>
In the process of producing a positive electrode, the configuration is the same as that of Example 1 except that the first positive electrode active material and the second positive electrode active material are mixed at a mass ratio of 4: 6 to prepare a mixture to prepare a positive electrode mixture slurry. A non-aqueous electrolyte secondary battery having the above was prepared. In the non-aqueous electrolyte secondary battery of Comparative Example 2, the electrolyte holding amount of the positive electrode was 0.655 g / cm ³ , and the electrolyte holding amount of the negative electrode was 0.628 g / cm ³ .

<Comparative example 3>
In the process of producing a positive electrode, a layered lithium transition metal _{represented by the composition formula Li 1.054} Ni _0.199 Co _0.597 Mn _0.199 Zr _0.005 O ₂ and having a pore volume V _100N of 5 mm ^{3 / g.} A non-aqueous electrolyte secondary battery having the same configuration as that of Example 1 was produced except that the oxide was used as the first positive electrode active material. In the non-aqueous electrolyte secondary battery of Comparative Example 3, the electrolyte holding amount of the positive electrode was 0.655 g / cm ³ , and the electrolyte holding amount of the negative electrode was 0.628 g / cm ³ .

<Comparative example 4>
In the production of the non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery having the same configuration as that of Example 1 was produced except that the pressure for rolling the positive electrode mixture layer was adjusted. In the non-aqueous electrolyte secondary battery of Comparative Example 4, the electrolyte holding amount of the positive electrode was 0.450 g / cm ³ , and the electrolyte holding amount of the negative electrode 14 was 0.620 g / cm ³ .

<Comparative example 5>
In the production of the non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery having the same configuration as that of Example 1 was produced except that the pressure for rolling the positive electrode mixture layer was adjusted. In the non-aqueous electrolyte secondary battery of Comparative Example 5, the electrolyte holding amount of the positive electrode was 0.400 g / cm ³ , and the electrolyte holding amount of the negative electrode was 0.620 g / cm ³ .

[Battery test]
The evaluation test shown below was carried out using the non-aqueous electrolyte secondary batteries of each Example and each Comparative Example prepared as described above.

(1) High-rate property test Each battery was charged to a SOC (charging depth) of 20% with a charging current of 1 C in a temperature atmosphere of 25 ° C. After that, the charge / discharge current is increased in the order of 5C discharge step → 5C charge step → 10C discharge step → 10C charge step → 15C discharge step → 15C charge step → 20C discharge step → 20C charge step → 25C discharge step → 25C charge step. I let you. At this time, the charging or discharging time in each step was 30 seconds, and a rest period of 15 minutes was provided between each step. That is, the charge / discharge cycle was performed in the order of 30-second discharge → 15-minute pause → 30-second charge → 15-minute pause. Then, in this charge / discharge cycle, the battery voltage at the time when the discharge time elapses for 10 seconds is plotted against the discharge current, and the current value when 1.5 V is reached from the straight line obtained by the minimum square method is calculated. The resistance value obtained from the current value was obtained as the output value of each non-aqueous electrolyte secondary battery. Based on the resistance value obtained for each non-aqueous electrolyte secondary battery, the durability against the high rate characteristic test was evaluated according to the following criteria.

◯: The resistance value after the high-rate characteristic test when Example 1 is 100 is less than 104% ×: The resistance value after the high-rate characteristic test when Example 1 is 100 is 104% or more. The evaluation results of the resistance value and the high rate characteristic obtained for the non-aqueous electrolyte secondary battery of each example and each comparative example are shown.

(2) Durability test In a temperature atmosphere of 25 ° C., the battery was charged to a voltage of 80% SOC with a charging current of 1C. Next, a partial charge / discharge cycle test was conducted in which a cycle of discharging to a voltage at which SOC becomes 20% with a discharge current of 5C and then charging to SOC 80% with a charging current of 5C was repeated in a temperature atmosphere of 60 ° C. .. This partial charge / discharge cycle was repeated until the ratio of the output to the output at the start of the partial charge / discharge cycle (initial output ratio) became 80%, and the total discharge amount until the initial output ratio became 80% was determined. Based on the total discharge amount at this time, the durability against the charge / discharge cycle was evaluated according to the following criteria.

◯: Total discharge amount after durability test when Example 1 is 100 or more ×: Total discharge amount after durability test when Example 1 is 100 is less than 95% Table 1 shows. The total discharge amount and the evaluation result obtained for the non-aqueous electrolyte secondary battery of each Comparative Example except for each Example and Comparative Example 5 are shown.

(3) Good winding rate test For the purpose of confirming the uniformity of the thickness of the positive electrode and the negative electrode, the good winding rate of the electrode bodies produced in Examples and Comparative Examples was evaluated. More specifically, with respect to the electrode bodies produced in each Example and each Comparative Example, the maximum value (winding deviation) of the deviation width in the axial direction of the winding structure of the positive electrode, the negative electrode and the separator was measured. The smaller the unwinding, the higher the uniformity of the thickness of the positive electrode or the negative electrode, that is, the thickness of the positive electrode mixture layer and the negative electrode mixture layer. As described above, when the thicknesses of the positive electrode and the negative electrode become non-uniform, it is considered that the deterioration of the active material is locally accelerated and the durability of the non-aqueous electrolyte secondary battery is lowered. Therefore, it is considered that the durability of the non-aqueous electrolyte secondary battery can be evaluated by confirming the uniformity of the thickness of each mixture layer in the positive electrode and the negative electrode by measuring the unwinding of the electrode body.

In this measurement test, in each electrode body, those having a winding deviation within ± 1 mm were evaluated as "pass", and those not within the range were evaluated as "fail". For each Example and each Comparative Example, the winding deviation of 50 electrode bodies was measured, and the ratio (winding non-defective product rate) to the total number of electrode bodies whose evaluation of the winding deviation was "pass" was obtained. .. Based on the obtained non-defective winding rate, the durability of the non-aqueous electrolyte secondary batteries of Examples and Comparative Examples was evaluated according to the following criteria.

◯: The good winding rate when Example 1 is 100 or more ×: The good winding rate when Example 1 is 100 is less than 95% Table 1 shows each Example and each Comparative Example. , The viscosity of the positive electrode mixture slurry, the non-defective winding rate of the electrode body, and the evaluation result of durability based on the non-defective winding rate are shown.

Regarding Comparative Example 5, although the result of the high rate characteristic is shown, the result of the durability test is omitted. This is because, as in the non-aqueous electrolyte batteries of Comparative Examples 1, 3 and 4, when the result of the high rate characteristic (resistance) in Table 1 exceeds 100% with respect to Example 1, the durability is also less than 100%. This is because the result of the high rate characteristic (resistance) of Comparative Example 5 also exceeds 100%, and therefore the durability is estimated to be less than 100% of that of Example 1, so that the durability test is omitted.

As is clear from the results in Table 1, in the non-aqueous electrolyte secondary battery using lithium titanium composite oxide as the negative electrode active material, the first positive electrode active material having a _{pore volume V 100N} of 8 mm ^{3 / g or more and} It contains a second positive electrode active material having a pore volume V _100N of 5 mm ³ / g or less, a first / second pore volume ratio of 4 times or more, and a content of the first positive electrode active material of the first positive electrode. It is 30% by mass or less with respect to the total amount of the active material and the second positive electrode active material, and the holding amount of the non-aqueous electrolyte held by the positive electrode is 0.49 g / cm ³ or more per unit volume of the positive electrode mixture layer. The non-aqueous electrolyte secondary batteries of Examples 1 to 3 have higher rate characteristics, durability after a charge / discharge cycle, and a good winding rate as compared with Comparative Examples 1 to 5 which do not satisfy any of the above configurations. It turned out to be significantly better. A non-aqueous electrolyte secondary battery having an excellent winding non-defective rate is considered to have excellent durability of the non-aqueous electrolyte secondary battery because the thickness of the positive electrode and the negative electrode is excellent in uniformity.

10 Non-aqueous electrolyte secondary battery, 12 positive electrode, 14 negative electrode, 16 separator, 18 positive terminal, 20 negative electrode terminal, 22 sealing plate, 24 outer can, 26 electrode body, 28 bottom, 30 injection port, 32 gas discharge valve.

Claims (2)

A positive electrode having a positive electrode mixture layer containing a first positive electrode active material and a second positive electrode active material, and
A negative electrode having a negative electrode mixture layer containing a lithium-titanium composite oxide as a negative electrode active material,
With non-aqueous electrolyte,
^{The first positive electrode active material has a volume of 8 mm 3} / g or more per mass of pores having a pore diameter of 100 nm or less.
^{The second positive electrode active material has a volume of 5 mm 3} / g or less per mass of pores having a pore diameter of 100 nm or less.
The volume per mass of the pores having a pore diameter of 100 nm or less in the first positive electrode active material is four times or more the volume per mass of the pores having a pore diameter of 100 nm or less in the second positive electrode active material. And
The content of the first positive electrode active material is 30% by mass or less with respect to the total amount of the first positive electrode active material and the second positive electrode active material.
The amount held in the non-aqueous electrolyte cathode is held state, and are 0.49 g / cm ³ or more per unit volume of the positive electrode mixture layer,
The first both the positive electrode active material and the second cathode active material, in the general formula _{(1) Li 1 + x M} a O 2 + b ( formula (1), x, a and b, x + a = 1, -0 . Satisfying the conditions of 2 ≦ x ≦ 0.2 and −0.1 ≦ b ≦ 0.1, M is a metal element containing at least one element selected from the group consisting of Ni, Co, Mn and Al. A non-aqueous electrolyte secondary battery, which is a layered lithium transition metal oxide represented by). The non-aqueous electrolyte secondary battery according to claim 1, wherein both the first positive electrode active material and the second positive electrode active material have an average particle size of 2 μm or more.

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