JP2014112496A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery hardly causing generation of gas even in fast charging and high temperatures, thereby suppressed in swelling of a battery.SOLUTION: A nonaqueous electrolyte secondary battery 10 according to an embodiment of the present invention includes, as a positive electrode active material, a lithium nickel composite oxide represented by general formula: LiNiCoMO(where, 0.95≤x≤1.1, 0<y≤0.5, 0≤z<0.5 and 0.055≤y+z≤0.5 are satisfied, and M represents at least one selected from the group consisting of Al, Mn, Mg, Ca, Fe, Ti, Zn, Sr, Ba, Zr, Y, B and Ta), and includes, as a negative electrode active material, a mixture of a carbon material and at least one of metals or metal compounds. The load of a negative electrode (battery capacity/mass of a negative electrode active material) is 372 mAh/g or less and 300 mAh/g or more, and the volume energy density is 530 Wh/L or less and 250 Wh/L or more.

Description

  The present invention relates to a non-aqueous electrolyte secondary battery in which battery swelling is suppressed.

  In recent years, portable devices such as mobile phones, smartphones, and digital cameras have increased power consumption due to the high functionality of these devices. Therefore, non-aqueous electrolyte secondary batteries used as power sources for these devices are also required to have a high capacity. On the other hand, due to the thinning of portable devices, there is a high demand for thinning of the battery itself, and in addition to the thinning in the initial state, the swelling of the battery is suppressed even after repeated charge / discharge after storage at high temperature. It is requested. Since the rectangular nonaqueous electrolyte secondary battery is likely to swell in the long-side exterior portion as compared with the cylindrical nonaqueous electrolyte secondary battery, this problem appears remarkably.

  The increase in capacity of the nonaqueous electrolyte secondary battery can be dealt with by using a nickel-based positive electrode active material. However, the non-aqueous electrolyte secondary battery using a nickel-based positive electrode active material has high reactivity between the positive electrode active material or the negative electrode active material and the non-aqueous electrolyte, and gas is generated during storage or during the cycle. The increase in battery thickness due to is a problem. In order to deal with such problems, for example, as disclosed in Patent Document 1 below, an additive is added to the non-aqueous electrolyte, and the reaction between the positive electrode active material or the negative electrode active material and the non-aqueous electrolyte is performed. The generation of gas is suppressed by suppressing the decomposition reaction of the non-aqueous electrolyte caused by the above.

JP 2010-140737 A

  When an additive is added to the non-aqueous electrolyte, a protective film is formed on the surface of the positive electrode active material or the negative electrode active material during the initial charge. The decomposition reaction of the water electrolyte can be suppressed. However, at the time of rapid charging, there is a problem that lithium is not taken into the negative electrode but is deposited outside the negative electrode, and the battery bulges due to gas generation.

  According to the nonaqueous electrolyte secondary battery of one embodiment of the present invention, even during rapid charging, lithium is difficult to deposit outside the negative electrode, gas is not easily generated, and battery swelling is suppressed. Next battery can be provided.

The nonaqueous electrolyte secondary battery of one embodiment of the present invention is
A positive electrode plate, a negative electrode plate, a non-aqueous electrolyte and a separator;
The positive electrode plate contains, as a positive electrode active material, a lithium nickel composite oxide represented by the following general formula (1),
Li _x Ni _1-yz Co _y M _z O ₂ (1)
(However, 0.95 ≦ x ≦ 1.1, 0 <y ≦ 0.5, 0 ≦ z <0.5, 0.055 ≦ y + z ≦ 0.5, M is Al, Mn, Mg, Ca, At least one selected from the group consisting of Fe, Ti, Zn, Sr, Ba, Zr, Y, B and Ta)
The negative electrode plate includes a mixture of a carbon material and at least one of a metal or a metal compound as a negative electrode active material,
The negative electrode load (battery capacity / negative electrode active material mass) is 372 mAh / g or less, 300 mAh / g or more,
The volume energy density is 530 Wh / L or less and 250 Wh / L or more.

  According to the non-aqueous electrolyte secondary battery of one embodiment of the present invention, since there is room for lithium uptake of the negative electrode active material, it is difficult for lithium to precipitate on the surface of the negative electrode active material even during rapid charging. Thus, a non-aqueous electrolyte secondary battery in which battery swelling is suppressed is obtained.

It is a disassembled perspective view of the square nonaqueous electrolyte secondary battery common to each experiment example.

  Hereinafter, the form for implementing this invention is demonstrated in detail using various experiment examples. However, the experimental examples shown below show an example of a prismatic nonaqueous electrolyte secondary battery for embodying the technical idea of the present invention, and the present invention is limited to any of these experimental examples. However, the present invention can be equally applied to various modifications without departing from the technical idea shown in the claims.

  The term “square” in the present invention is used to mean not only a perfect rectangular parallelepiped, but also includes those in which both side end faces in the width direction have a round shape and those in which the corners on both side end faces are rounded. It has been. In each experimental example, a square nonaqueous electrolyte secondary battery in which both end faces in the width direction have a round shape will be representatively described. First, a specific method for manufacturing the prismatic nonaqueous electrolyte secondary battery according to Experimental Example 1 will be described.

[Experimental Example 1]
[Preparation of positive electrode active material]
The lithium nickel cobalt aluminum composite oxide as the positive electrode active material was obtained as follows. As a starting material, lithium hydroxide (LiOH.H ₂ O) was used as a lithium source. As the transition metal source, nickel, cobalt and aluminum coprecipitated hydroxides (Ni _0.8 Co _0.15 Al _0.05 (OH) ₂ ) were used. These were weighed and mixed so that the molar ratio of lithium to transition metal (nickel, cobalt and aluminum) was 1: 1. The obtained mixture was baked at 400 ° C. for 12 hours in an oxygen atmosphere, crushed in a mortar, and further baked at 900 ° C. for 24 hours in an oxygen atmosphere to obtain LiNi _0.8 Co _0.15 Al _0.05 O. A lithium nickel cobalt aluminum composite oxide represented by ₂ was obtained. This was pulverized in a mortar to obtain a positive electrode active material used in each experimental example. The chemical composition of the lithium nickel cobalt aluminum composite oxide was measured by ICP (Inductively Coupled Plasma).

[Preparation of positive electrode mixture slurry]
The carbon powder as the conductive agent is 2.5 parts by mass and the polyvinylidene fluoride powder as the binder is 2 parts by mass with respect to 95 parts by mass of the lithium nickel cobalt aluminum composite oxide as the positive electrode active material obtained as described above. It mixed so that it might become 0.5 mass part, this was mixed with the N-methylpyrrolidone (NMP) solution, and the positive mix slurry was prepared.

[Preparation of positive electrode plate]
The positive electrode mixture slurry obtained as described above was applied to both surfaces of an aluminum foil as a positive electrode core having a thickness of 15 μm by the doctor blade method and then dried, whereby a positive electrode mixture layer was formed on both surfaces of the positive electrode core. Formed. Subsequently, it compressed until it became predetermined thickness using a compression roller, and produced the positive electrode plate of length about 670 mm and width about 58 mm. Next, the positive electrode core was exposed at one end in the longitudinal direction, and one end of an aluminum positive electrode lead having a length of 30 mm, a width of 3 mm, and a thickness of 0.1 mm was attached to this portion by ultrasonic welding.

[Production of negative electrode plate]
As a negative electrode active material, a compound in which artificial graphite having an average particle diameter of 20 μm and SiOx (x = 1) having an average particle diameter of 10 μm are coated with a carbon material (a composite in which 10% by mass of the entire composite is a carbon material) ) Was mixed so that the content ratio of SiO was 3% by mass by mass ratio. 100 parts by mass of the negative electrode active material, 1 part by mass of styrene-butadiene copolymer (BM-400B manufactured by Nippon Zeon Co., Ltd.) as a binder, and 1 part by mass of carboxymethyl cellulose as a thickener An appropriate amount of water was mixed to prepare a negative electrode mixture paste.

  This negative electrode mixture paste was applied to both surfaces of a copper foil as a negative electrode core having a thickness of 10 μm, and then dried to form a negative electrode mixture layer on both surfaces of the negative electrode core. Subsequently, it compressed until it became predetermined thickness using a compression roller, and produced the negative electrode plate about 650 mm in length and about 60 mm in width. Next, the negative electrode core was exposed at one end portion in the longitudinal direction, and one end of a nickel negative electrode lead having a length of 30 mm, a width of 3 mm, and a thickness of 0.1 mm was attached to this portion by ultrasonic welding.

[Preparation of non-aqueous electrolyte]
With respect to a solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed at a volume ratio of 1: 4 at 25 ° C., the concentration of lithium hexafluorophosphate (LiPF ₆ ) is 1 mol / L. The nonaqueous electrolyte solution used for each experimental example was prepared.

[Preparation of non-aqueous electrolyte battery]
The positive electrode plate and the negative electrode plate manufactured as described above are arranged such that the positive electrode lead is on the winding end side and the negative electrode lead is on the winding start end side, and the positive electrode lead and the negative electrode lead extend in the same direction. Thus, the flat wound electrode body used in Experimental Example 1 was manufactured by winding in a flat shape through a separator made of a polyethylene microporous membrane.

  The process of assembling the nonaqueous electrolyte secondary battery 10 of Experimental Example 1 using the flat wound electrode body produced as described above will be described with reference to FIG. The flat wound electrode body 11 is provided with a positive electrode lead 12 and a negative electrode lead 13 at one end in the winding axis direction. An upper insulating gasket 15 made of polypropylene sulfide (PPS) was disposed on the upper surface of the aluminum sealing plate 14, and a current collecting plate 17 was disposed on the lower surface via a lower insulating gasket 16 made of PPS. Then, the upper insulating gasket 15, the lower insulating gasket 16 and the current collecting plate 17 are fixed to the sealing plate 14 by caulking the rivet terminal 19 in the terminal through hole 18 formed in the center in the longitudinal direction of the sealing plate 14. Thus, an assembly sealing body 20 was produced.

  The flat wound electrode body 11 was accommodated in a rectangular battery outer can 21 (aluminum, thickness: 300 μm), and then the produced assembly sealing body 20 was mounted. At that time, the positive electrode lead 12 and the negative electrode lead 13 were pushed through the respective through holes formed in the insulating case 22, and the assembly sealing body 20 was disposed on the opening side of the rectangular battery outer can 21. Subsequently, the other end of the positive electrode lead 12 was laser welded to the inner surface of the sealing plate 14, and the other end of the negative electrode lead 13 was laser welded to the current collector plate 17. Thereafter, the sealing plate 14 was disposed in the opening of the rectangular battery outer can 21, and the opening of the rectangular battery outer can 21 was sealed by laser welding the periphery of the sealing plate 14 to the rectangular battery outer can 21.

  Next, 5.0 g of non-aqueous electrolyte is injected into the rectangular battery outer can 21 from the liquid injection port 23 of the sealing plate 14, the liquid injection port 23 is fitted with the plug 24, and the plug 24 is connected by laser welding. The sealing plate 14 was welded to seal the liquid injection port 23. In this way, the battery size is thickness: about 6.5 mm, width: about 38 mm, height: 64 mm, theoretical capacity is 2050 mAh, volumetric energy density is 450 Wh / L, negative electrode load (battery capacity / negative electrode) A square nonaqueous electrolyte secondary battery 10 of Experimental Example 1 having an active material mass of 300 mAh / g was produced.

  The theoretical capacity of graphite as the negative electrode active material is 372 mAh / g, and the theoretical capacity of SiO is larger than the theoretical capacity of graphite. Therefore, the negative electrode load in the prismatic nonaqueous electrolyte secondary battery 10 of Embodiment 1 is 300 mAh / g, which means that the amount of the negative electrode active material used in the prismatic nonaqueous electrolyte secondary battery 10 is large. This means that even when the positive electrode active material is fully charged, there are many uncharged negative electrode active materials.

[Experiment 2]
The prismatic nonaqueous electrolyte secondary was the same as Experimental Example 1 except that the theoretical capacity was 2050 mAh (volume energy density 450 Wh / L), the negative electrode coating mass was adjusted, and the negative electrode load was 330 mAh / g. A battery was produced. The specific configuration of the prismatic nonaqueous electrolyte secondary battery of Experimental Example 2 is the same as that of the prismatic nonaqueous electrolyte secondary battery 10 of Experimental Example 1 shown in FIG. Is omitted (hereinafter the same applies to Experimental Examples 3 to 12).

[Experiment 3]
The prismatic nonaqueous electrolyte secondary was the same as Experimental Example 1 except that the theoretical capacity was 2050 mAh (volume energy density 450 Wh / L), the negative electrode coating mass was adjusted, and the negative electrode load was 372 mAh / g. A battery was produced.

[Experimental Example 4]
Except for adjusting the coating mass of the positive electrode to a theoretical capacity of 2350 mAh (volume energy density 530 Wh / L) and adjusting the negative electrode coating mass to a negative electrode load of 330 mAh / g, the same as in Experimental Example 1 above. Thus, a square nonaqueous electrolyte secondary battery was produced.

[Experimental Example 5]
The mixing ratio of the negative electrode active material was the same as in Experimental Example 2 except that a negative electrode active material was used in which the synthetic graphite was 98% by mass and the SiO was coated with a carbon material on the surface of 2% by mass. A rectangular nonaqueous electrolyte secondary battery was produced.

[Experimental Example 6]
The negative electrode active material was mixed in the same manner as in Experimental Example 2 except that the negative electrode active material was mixed with 96% by mass of artificial graphite and 4% by mass of a compound whose surface was coated with a carbon material on SiO. A square nonaqueous electrolyte secondary battery was produced.

[Experimental Example 7]
Except for using a negative electrode active material in which the mixing ratio of the negative electrode active material was 99% by mass of artificial graphite and 1% by mass of a compound in which the surface of SiO was coated with a carbon material, the same as in Experimental Example 2 above. A square nonaqueous electrolyte secondary battery was produced.

[Experimental Example 8]
The negative electrode active material was mixed in the same manner as in Experimental Example 2 except that the negative electrode active material was 95% by mass of artificial graphite and 5% by mass of the compound whose surface was coated with a carbon material on SiO. A square nonaqueous electrolyte secondary battery was produced.

[Experimental Example 9]
A square nonaqueous electrolyte secondary battery was produced in the same manner as in Experimental Example 2 except that only artificial graphite having an average particle size of 20 μm was used as the negative electrode active material.

[Experimental Example 10]
The prismatic nonaqueous electrolyte secondary was the same as Experimental Example 1 except that the theoretical capacity was 2050 mAh (volume energy density 450 Wh / L), the negative electrode coating mass was adjusted, and the negative electrode load was 250 mAh / g. A battery was produced.

[Experimental Example 11]
A square nonaqueous electrolyte secondary, as in Experimental Example 1, except that the theoretical capacity is 2050 mAh (volume energy density 450 Wh / L), the negative electrode coating mass is adjusted, and the negative electrode load is 390 mAh / g. A battery was produced.

[Experimental example 12]
The same as Experimental Example 1 except that the coating mass of the positive electrode was adjusted, the theoretical capacity was 2550 mAh (volume energy density 580 Wh / L), the negative electrode coating mass was adjusted, and the negative electrode load was 330 mAh / g. Thus, a square nonaqueous electrolyte secondary battery was produced.

[Cycle test]
About each square nonaqueous electrolyte secondary battery of the said Experimental Examples 1-12, five each were prepared and the cycle characteristic was evaluated as follows. In a constant temperature bath maintained at 25 ° C., constant current charging was performed until the battery voltage became 4.2 V at 0.7 It, and then constant voltage charging was performed until the current decreased to 0.05 It at 4.2 V, and then The battery was discharged at a constant current until the battery voltage became 2.5 V at 1.0 It. This charging / discharging was made into 1 cycle and repeated 500 cycles. Then, by measuring the discharge capacity at the first cycle and the discharge capacity at the 500th cycle, the capacity retention rate as the cycle characteristics was obtained by the following calculation formula.
Capacity maintenance rate (%)
= (Discharge capacity at 500th cycle / discharge capacity at the first cycle) × 100

Moreover, the battery thickness A after the first charge and the thickness B after the charge after 500 cycles were measured, and the amount of swelling (%) of the battery was calculated by the following formula. The results are summarized in Table 1.
Battery swelling (%) = ((B−A) / A)) × 100

  From the results shown in Table 1, the following can be understood. That is, the results of Experimental Examples 1 to 8 including SiO in the negative electrode active material have a higher capacity retention rate after 500 cycles than the results of Experimental Example 9 that does not include SiO in the negative electrode active material. It is getting smaller. This is because the amount of lithium that can be accepted by the negative electrode active material increases by adding SiO, which has a theoretical capacity larger than that of graphite, to the negative electrode active material. This is considered to be because the negative electrode active material accompanying the charge / discharge was prevented from collapsing due to expansion and contraction, and the cycle characteristics were improved. In addition, since the deposition of lithium due to the negative electrode active material being unable to accept lithium is suppressed, the generation of gas is suppressed and the swelling of the battery is also reduced.

  Further, the results of Experimental Examples 1 to 3 and the results of Experimental Examples 10 and 11 in which the SiO content in the negative electrode active material is 3% by mass and the battery energy density is 450 Wh / L, but only the negative electrode load is different. In contrast, it can be seen that the negative electrode load design is preferably 372 mAh / g or less and 300 mAh / g or more. This is because if the negative electrode load is designed to exceed the theoretical capacity of the carbon material, 372 mAh / g, the negative electrode active material cannot accept lithium, lithium is deposited, cycle characteristics deteriorate, and gas is generated. This is probably because the amount of the battery increases and the swelling of the battery also increases.

  In order to reduce the load on the negative electrode, it is necessary to increase the content of the negative electrode active material. In this case, since the internal space of the battery is determined, it is possible to reduce the load on the negative electrode by increasing the density of the negative electrode. However, if the density of the negative electrode is increased, the non-aqueous electrolyte solution of the wound electrode body It becomes difficult to penetrate to the inside, and the amount of inactive negative electrode active material in which the nonaqueous electrolyte does not exist in the surroundings increases. Therefore, even when the load on the negative electrode is reduced and designed to be less than 300 mAh / g, lithium is not accepted and lithium is deposited, so that the cycle characteristics deteriorate, the amount of gas generated increases, and the battery swells. It is thought that it will end up.

  Next, when the results of Experimental Examples 2 and 4 in which the SiO content in the negative electrode active material is 3% by mass and the negative electrode load is 330 mAh / g but only the energy density is different are compared with the results of Experimental Example 12, It can be seen that the energy density is desirably 530 Wh / L or less. In addition, when the energy density of the battery is less than 250 Wh / L, the swelling of the battery is equivalent to that in Experimental Example 9 using only graphite as the negative electrode active material. The demand for energy density cannot be met.

  In order to increase the energy density, it is necessary to increase the content of the positive electrode active material. In this case, since the internal space of the battery is determined, it is possible to increase the energy density by increasing the density of the positive electrode. However, if the positive electrode density is increased, the internal space of the wound electrode body does not move toward the negative electrode side. The water electrolyte turns. Therefore, when the volume energy density exceeds 530 Wh / L, the deterioration of the positive electrode active material is accelerated, the cycle characteristics are deteriorated, the decomposition of the non-aqueous electrolyte is promoted, the gas generation is increased, and the battery is swollen. It is thought that it will increase.

  When comparing the results of Experimental Examples 2 and 5-8 in which the negative electrode load is 330 mAh / g and the energy density is 450 Wh / L, but only the SiO content in the negative electrode active material is different, the SiO in the negative electrode active material is compared. It can be seen that the content is preferably 2% by mass or more and 4% by mass or less. This result shows that when the amount of SiO is less than 2% by mass, the effect of adding SiO to the negative electrode active material is small, and when the amount of SiO exceeds 4% by mass, inactive SiO exists. This is probably because the effect of adding SiO is reduced.

In the above experimental examples 1 to 12, an example in which lithium nickel cobalt aluminum composite oxide (LiNi _0.8 Co _0.15 Al _0.05 O ₂ ) was used as the positive electrode active material was shown. In the present invention, A lithium nickel cobalt aluminum composite oxide having another composition may be used in which a part of cobalt in the lithium nickel cobalt aluminum composite oxide is replaced with another element. As the substitution element of cobalt, at least one selected from the group consisting of Al, Mn, Mg, Ca, Fe, Ti, Zn, Sr, Ba, Zr, Y, B, and Ta can be used. The lithium nickel cobalt aluminum composite oxide as the positive electrode active material has the formula Li _x Ni _1-yz Co _y M _z O ₂ (where 0.95 ≦ x ≦ 1.1, 0 <y ≦ 0.5, 0 ≦ z <0.5, 0.055 ≦ y + z ≦ 0.5, M is selected from the group consisting of Al, Mn, Mg, Ca, Fe, Ti, Zn, Sr, Ba, Zr, Y, B, and Ta. At least one selected) is preferred.

In the above experimental examples 1 to 12, examples in which a mixture of artificial graphite and SiOx (x = 1) particles was used as the negative electrode active material. However, in the present invention, natural graphite, carbon black, coke, glassy carbon, carbon fiber, etc., or a mixture of one or more of these fired bodies can be used instead of artificial graphite. Further, in place of particles of SiOx (x = 1), silicon (Si), silicon oxide (SiO _x , 0.5 ≦ x <1.6), tin (Sn) that can react with a larger amount of lithium than carbon. ), Aluminum (Al), Sb (antimony), or other metals or metal compounds may be used.

  In Examples 1 to 12 described above, EC and EMC were used as the nonaqueous solvent for the nonaqueous electrolytic solution. In addition, cyclic carbonates such as propylene carbonate (PC) and butylene carbonate (BC); Fluorinated cyclic carbonates; cyclic carboxylic acid esters such as γ-butyrolactone (γ-BL) and γ-valerolactone (γ-VL); dimethyl carbonate (DMC), diethyl carbonate (DEC), methylpropyl carbonate (MPC) ), Chain carbonates such as dibutyl carbonate (DBC); fluorinated chain carbonates; chain carboxylates such as methyl pivalate, ethyl pivalate, methyl isobutyrate, methyl propionate; Amide compounds such as N′-dimethylformamide and N-methyloxazolidinone; Sulfur compounds such as run; tetrafluoroborate 1-ethyl-3- ambient temperature molten salt such as methyl imidazolium; and the like can be used. Moreover, you may make it use these in mixture of 2 or more types.

An example of using lithium hexafluorophosphate (LiPF ₆ ) as an electrolyte salt to be dissolved in a non-aqueous solvent in a non-aqueous electrolyte has been shown, but in addition, it is generally used as an electrolyte salt in non-aqueous electrolyte secondary batteries. Lithium salts can be used. Examples of such lithium salts include LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ), LiC (CF ₃ SO ₂ ) ₃ , LiC (C ₂ F ₅ SO ₂ ) ₃ , LiAsF ₆ , LiClO ₄ , Li ₂ B ₁₀ Cl ₁₀ , Li ₂ B ₁₂ Cl ₁₂ or the like alone or from these What mixed multiple types can be used. The amount of electrolyte salt dissolved in the non-aqueous solvent is preferably 0.8 to 1.5 mol / L.

  In the electrolyte in the non-aqueous electrolyte, as the electrode stabilizing compound, for example, vinylene carbonate (VC), vinyl ethylene carbonate (VEC), succinic anhydride (SUCAH), maleic anhydride (MAAH), glycolic anhydride Products such as ethylene sulfite (ES), divinyl sulfone (VS), vinyl acetate (VA), vinyl pivalate (VP), catechol carbonate, biphenyl (BP) and the like may be added. Two or more of these compounds may be appropriately mixed and used.

  As a separator, the separator conventionally used can be used. Specifically, not only a separator made of polyethylene, but also a material in which a layer made of polypropylene is formed on the surface of a polyethylene layer, or a material in which a resin such as an aramid resin is applied to the surface of a polyethylene separator is used. Also good.

  In Examples 1 to 12 described above, the case of a rectangular nonaqueous electrolyte secondary battery has been described. However, the present invention can also be applied to a cylindrical nonaqueous electrolyte secondary battery. However, since the swelling of the battery is larger in the case of the rectangular non-aqueous electrolyte secondary battery than in the case of the cylindrical non-aqueous electrolyte secondary battery, the present invention is particularly effective when applied to the rectangular non-aqueous electrolyte secondary battery. Appears prominently.

DESCRIPTION OF SYMBOLS 10 ... Non-aqueous electrolyte secondary battery 11 ... Flat winding electrode body 12 ... Positive electrode lead 13 ... Negative electrode lead 14 ... Sealing plate 15 ... Upper insulating gasket 16 ... Lower insulating gasket 17 ... Current collector plate 18 ... Terminal through-hole 19 ... Rivet terminal 20 ... Assembly sealing body 21 ... Square battery outer can
22 ... Insulating case 23 ... Injection port 24 ... Sealing plug

Claims (4)

A positive electrode plate, a negative electrode plate, a non-aqueous electrolyte and a separator;
The positive electrode plate contains, as a positive electrode active material, a lithium nickel composite oxide represented by the following general formula (1),
Li _x Ni _1-yz Co _y M _z O ₂ (1)
(However, 0.95 ≦ x ≦ 1.1, 0 <y ≦ 0.5, 0 ≦ z <0.5, 0.055 ≦ y + z ≦ 0.5, M is Al, Mn, Mg, Ca, At least one selected from the group consisting of Fe, Ti, Zn, Sr, Ba, Zr, Y, B and Ta)
The negative electrode plate includes a mixture of a carbon material and at least one of a metal or a metal compound as a negative electrode active material,
The negative electrode load (battery capacity / negative electrode active material mass) is 372 mAh / g or less, 300 mAh / g or more,
Volume energy density is 530 Wh / L or less, 250 Wh / L or more,
Non-aqueous electrolyte secondary battery.   The nonaqueous electrolyte secondary battery according to claim 1, which is a square shape. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode active material is a mixture of a carbon material and SiO _x (0.5 ≦ x <1.6). 4. The non-aqueous electrolyte 2 according to claim 3, wherein the negative electrode active material contains 2% by mass to 4% by mass of SiO _x (0.5 ≦ x <1.6) with respect to the total mass of the negative electrode active material. Next battery.

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