JP2009266706A - Lithium-ion secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithium-ion secondary battery that prevents the decrease in battery output so as to improve life characteristics. <P>SOLUTION: The lithium-ion secondary battery 20 includes an electrode group 6 in which a positive electrode plate W1 and a negative electrode plate W3 are winded via a separator W5 not so as to directly contact each other. The positive electrode plate W1 has positive-electrode active material compound W2 which contains lithium manganate used as positive-electrode active material and which is painted on both side of an aluminum foil thereof. The negative electrode plate W3 has negative-electrode active material compound W4 which contains an easily graphitizable carbon as negative-electrode active material and which is painted on both side of a rolling copper foil thereof. Thickness of the negative electrode plate W3 is manufactured such that the ratio of the discharge capacity of the negative electrode plate W3 to that of the positive electrode plate W1 is ≥1.0 and ≤1.3 after initial charging. In charging, the easily graphitizable carbon is used up to the low potential region, which reduces the expansion and contraction of the easily graphitizable carbon. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a lithium ion secondary battery, and in particular, a positive electrode in which an active material mixture containing a lithium transition metal composite oxide as a positive electrode active material is applied to a positive electrode current collector, and an active material mixture containing a negative electrode active material. The present invention relates to a lithium ion secondary battery having a negative electrode in which an agent is applied to a negative electrode current collector.

  Conventionally, in the field of rechargeable secondary batteries, aqueous batteries such as lead batteries, nickel-cadmium batteries, and nickel-hydrogen batteries have been mainstream. However, due to global warming and fuel depletion problems, electric vehicles and hybrid vehicles that use electric motors to assist a part of the drive have attracted attention, and the batteries used for the power supply have higher capacity and higher input / output. A new battery has been demanded. As a battery that meets such requirements, a non-aqueous lithium ion secondary battery having high voltage characteristics has attracted attention.

  Generally, a lithium transition metal composite oxide is used as a positive electrode material of a lithium ion secondary battery, and lithium cobalt oxide is used among them in terms of balance of capacity and cycle characteristics. However, since lithium cobaltate has a small amount of cobalt as a raw material and is expensive, lithium manganate is considered promising as a positive electrode material for batteries for electric vehicles and hybrid electric vehicles.

  On the other hand, negative electrode materials for lithium ion secondary batteries for electric vehicles and hybrid electric vehicles are required to have high input / output characteristics. Therefore, non-graphitizable carbon materials obtained by firing furan resins such as furfuryl alcohol are generally used. It is used for. The non-graphitizable carbon material fired from synthetic resin has a feature that it has a capacity higher than the theoretical capacity value of graphite-based materials, has excellent cycle characteristics, and has high input / output characteristics. It is a material that has been. A technique for improving the energy density and capacity of a battery by making a non-graphitizable carbon material into a specific crystal structure is disclosed (for example, see Patent Document 1).

Japanese Patent Application Laid-Open No. 11-337995

  However, the technique of Patent Document 1 has a drawback that it is difficult to increase the capacity of the battery because the irreversible capacity of the non-graphitizable carbon material used as the negative electrode active material increases. The charge / discharge characteristics of non-graphitizable carbon materials include a constant voltage region where the potential is almost constant with respect to capacity change and a constant current region where the potential increases with increasing capacity. In order to improve, the charging / discharging range is set to a constant current region while avoiding the constant voltage region. In this case, if the material has a large constant voltage region, this portion is not used, so that unnecessary preparation is made and the discharge capacity of the battery is reduced. Furthermore, since the potential of the negative electrode is increased by using the constant current region and the open circuit voltage is decreased as a battery, the voltage difference up to the lower limit voltage is reduced and the output is also decreased. Although an additive is added to the electrolyte to reduce the irreversible capacity of the non-graphitizable carbon material and to suppress the decomposition of the electrolyte, a temporary effect to improve the discharge capacity and life characteristics is recognized, but the additive is expensive. Many of them are expensive. When an easily graphitizable carbon material is used as the negative electrode active material instead of such a non-graphitizable carbon material, the capacity per unit weight is smaller than that of the non-graphitizable carbon material, but the cycle life is reduced. The characteristics will also deteriorate.

  An object of the present invention is to provide a lithium ion secondary battery that can suppress a decrease in battery output and improve life characteristics.

  In order to solve the above problems, the present invention provides a positive electrode in which an active material mixture including a lithium transition metal composite oxide as a positive electrode active material is applied to a positive electrode current collector, and an active material mixture including a negative electrode active material In a lithium ion secondary battery having a negative electrode coated on a negative electrode current collector, a graphitizable carbon material is used as the negative electrode active material, and the negative electrode with respect to the discharge capacity of the positive electrode after initial charge The ratio of the discharge capacity is 1.0 or more and 1.3 or less.

  In the present invention, an easily graphitizable carbon material is used as the negative electrode active material, and the ratio of the discharge capacity of the negative electrode to the discharge capacity of the positive electrode is 1.0 or more and 1.3 or less, so that the low potential region of the graphitizable carbon material is reduced. Can be used for charging and discharging, the battery voltage can be increased by the potential difference between the positive electrode and the negative electrode to improve the battery output, and the expansion and shrinkage of the graphitizable carbon material can be suppressed in the low potential region to improve the battery life. it can.

  In this case, if the graphitizable carbon material has an initial charge capacity of 250 mAh / g or more and 350 mAh / g or less, and the ratio of the discharge capacity to the initial charge capacity is 0.85 or more, the working potential of the graphitizable carbon material is used. Since the area is optimized, the output and cycle characteristics can be improved. Moreover, if the ratio of the discharge capacity of 0 V to 0.2 V to the discharge capacity of 0.2 V to 1.0 V of the graphitizable carbon material is 1.0 or less, decomposition of the electrolyte in the negative electrode is suppressed, and cycle characteristics are improved. This can be further improved.

  According to the present invention, an easily graphitizable carbon material is used as the negative electrode active material, and the ratio of the discharge capacity of the negative electrode to the discharge capacity of the positive electrode is 1.0 or more and 1.3 or less. Used for charging / discharging up to the potential range, the battery voltage rises due to the potential difference between the positive and negative electrodes, and the battery output can be improved, and the expansion and contraction of the graphitizable carbon material is suppressed and the battery life is improved in the low potential range. Can be obtained.

  Embodiments of a cylindrical lithium ion secondary battery to which the present invention is applied will be described below with reference to the drawings.

(Constitution)
As shown in FIG. 1, the cylindrical lithium ion secondary battery 20 of this embodiment includes an electrode group 6 in which strip-like positive and negative electrode plates are wound in a spiral shape with a separator interposed therebetween. The electrode group 6 is housed in an iron battery container 7 having a bottomed cylindrical shape and nickel plating.

  On the upper side of the electrode group 6, an aluminum positive electrode current collecting ring 4 for collecting the electric potential from the positive electrode plate W <b> 1 is disposed substantially on the extension line of the hollow cylindrical shaft core 1 made of polypropylene. The positive electrode current collecting ring 4 is fixed to the upper end portion of the shaft core 1. The edge part of the positive electrode lead piece 2 led out from the positive electrode plate W1 is joined to the periphery of the flange part integrally protruding from the periphery of the positive electrode current collecting ring 4 by ultrasonic welding. A disc-shaped battery lid serving as a positive electrode external terminal is disposed above the positive electrode current collecting ring 4. The battery lid includes an aluminum lid case 12, a lid cap 13, a valve retainer 14 that keeps airtightness, and a cleavage valve 11 that is cleaved by an increase in internal pressure, and these are laminated to form a peripheral edge of the lid case 12. It is assembled by caulking and fixing. One end of two positive electrode lead plates 9 formed by stacking a plurality of aluminum ribbons is fixed to the upper portion of the positive electrode current collecting ring 4, and another one is fixed to the lower surface of the lid case 12. One end of the book is welded. The other ends of the two positive electrode lead plates 9 are connected by welding.

  On the other hand, a negative electrode current collector ring 5 made of copper for collecting the electric potential from the negative electrode plate W3 is disposed below the electrode group 6. The outer peripheral surface of the lower end portion of the shaft core 1 is fixed to the inner peripheral surface of the negative electrode current collecting ring 5. The outer peripheral edge of the negative electrode current collecting ring 5 is welded with the end of the negative electrode lead piece 3 led out from the negative electrode plate W3. A copper negative electrode lead plate 8 for electrical conduction is welded to the lower portion of the negative electrode current collecting ring 5, and the negative electrode lead plate 8 is welded to the inner bottom portion of the battery container 7. In this example, the dimensions of the battery container 7 are set to an outer diameter of 40 mm and an inner diameter of 39 mm.

The battery lid is caulked and fixed to the upper part of the battery container 7 via an insulating and heat resistant EPDM resin gasket 10. For this reason, the inside of the lithium ion secondary battery 20 is sealed. Further, a non-aqueous electrolyte solution (not shown) is injected into the battery container 7. Non-aqueous electrolyte includes hexafluorophosphoric acid as a lithium salt in a mixed solvent in which ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) are mixed at a volume ratio of 1: 1: 1. lithium (LiPF ₆₎ which was dissolved 1 mol / l is used.

  The electrode group 6 is wound through a separator W5 so that the positive electrode plate W1 and the negative electrode plate W3 are not in direct contact with each other. At this time, the positive electrode lead piece 2 and the negative electrode lead piece 3 are wound so as to be located on both end surfaces of the electrode group 6 on the opposite sides. For the separator W5, a polyethylene film is used, and in this example, the width is set to 90 mm and the thickness is set to 40 μm. In addition, an insulation coating is applied to the entire circumference of the collar portion peripheral surface of the electrode group 6 and the positive electrode current collecting ring 4. For the insulation coating, an adhesive tape in which a hexamethacrylate adhesive is applied to one side of a polyimide base material is used. The pressure-sensitive adhesive tape is wound one or more times from the collar surface to the outer circumferential surface of the electrode group 6. The diameter of the electrode group 6 is set to 38 ± 0.1 mm by adjusting the lengths of the positive electrode plate W1, the negative electrode plate W3, and the separator W5.

  The positive electrode plate W1 constituting the electrode group 6 has an aluminum foil as a positive electrode current collector. In this example, the aluminum foil is set to a thickness of 20 μm. A positive electrode active material mixture W2 containing lithium manganate as a lithium transition metal composite oxide of the positive electrode active material is applied to both surfaces of the aluminum foil. In the positive electrode active material mixture W2, for example, 10 parts by weight of a conductive graphite flake graphite and a binder (binder) polyvinylidene fluoride (hereinafter abbreviated as PVDF) with respect to 100 parts by weight of lithium manganate. 5) parts by weight. When the positive electrode active material mixture W2 is applied to the aluminum foil, a dispersion solvent N-methylpyrrolidone (hereinafter abbreviated as NMP) is used. An uncoated portion of the positive electrode active material mixture W2 having a width of 30 mm is formed on the side edge on one side in the longitudinal direction of the aluminum foil. The uncoated portion is cut out in a comb shape (rectangular shape), and the positive electrode lead piece 2 is formed in the remaining portion of the cutout. The interval between the adjacent positive electrode lead pieces 2 is set to 50 mm, and the width of the positive electrode lead piece 2 is set to 5 mm. After drying, the positive electrode plate W1 is pressed by a heatable roll press so that the thickness becomes 90 μm, and the width is cut to 82 mm.

  On the other hand, the negative electrode plate W3 has a rolled copper foil as a negative electrode current collector. In this example, the rolled copper foil is set to a thickness of 10 μm. A negative electrode active material mixture W4 containing an easily graphitizable carbon material capable of occluding and releasing lithium ions as a negative electrode active material is applied to both surfaces of the rolled copper foil. In the negative electrode active material mixture W4, for example, 10 parts by weight of PVDF as a binder is blended with 90 parts by weight of the graphitizable carbon material. When the negative electrode active material mixture W4 is applied to the rolled copper foil, NMP as a dispersion solvent is used. An uncoated portion of the negative electrode active material mixture W4 with a width of 30 mm is formed on the side edge on one side in the longitudinal direction of the rolled copper foil, and the negative electrode lead piece 3 is formed. Yes. The interval between the adjacent negative electrode lead pieces 3 is set to 50 mm, and the width of the negative electrode lead piece 3 is set to 5 mm. The negative electrode plate W3 is dried and then pressed in the same manner as the positive electrode plate W1, and the width is cut to 86 mm. The thickness of the negative electrode plate W3 is such that the ratio of the discharge capacity of the negative electrode plate W3 to the discharge capacity of the positive electrode plate W1 after the initial charge (negative electrode discharge capacity / positive electrode discharge capacity ratio) is 1.0 or more and 1.3 or less. Has been prepared.

  The negative electrode active material mixture W4 has an initial charge capacity of 250 mAh / g or more and 350 mAh / g or less, and a ratio of the discharge capacity to the initial charge capacity (discharge capacity / initial charge capacity ratio) of 0.85 or more, 0.2 V Graphitized charcoal having a ratio of 0 V to 0.2 V discharge capacity to 0 V to 1.0 V discharge capacity (0 V to 0.2 V discharge capacity / 0.2 V to 1.0 V discharge capacity ratio) of 1.0 or less The material is used. The graphitizable carbon material is obtained by heat-treating a pitch at about 1000 ° C. Since the capacity characteristics of the graphitizable carbon material obtained vary depending on the pitch components and heat treatment conditions, materials satisfying the above-described ratios can be selected.

(Battery assembly)
The lithium ion secondary battery 20 is assembled in the following procedure. That is, the positive electrode plate W1 and the negative electrode plate W3 are wound around the shaft core 1 by the winding device through the separator W5 to produce the electrode group 6. At this time, the positive electrode lead piece 2 and the negative electrode lead piece 3 are respectively positioned on opposite end surfaces of the wound group 6. The positive electrode lead piece 2 and the negative electrode lead piece 3 are welded to the positive electrode current collecting ring 4 and the negative electrode current collecting ring 5, respectively. At this time, the positive electrode lead piece 2 and the negative electrode lead piece 3 are respectively deformed, gathered and brought into contact with the vicinity of the buttocks integrally projecting from the periphery of the positive electrode current collecting ring 4 and the negative electrode current collecting ring 5, and then subjected to ultrasonic waves They were joined by welding. After the insulating coating was applied to the entire circumference of the collar peripheral surface of the positive electrode current collecting ring 4, the wound group 6 was inserted into the battery container 7. A negative electrode lead plate 8 pre-welded to the negative electrode current collecting ring 5 is welded to the inner bottom portion of the battery container 7. In order to crimp and fix the battery lid at a position 9 mm below the upper end of the battery container 7, a stepped portion is formed to form a stepped portion. After connecting the positive electrode current collecting ring 4 and the battery lid with the positive electrode lead plate 9, a nonaqueous electrolytic solution is injected into the battery container 7 from the hollow portion of the shaft core 1 to infiltrate the electrode group 6 into the nonaqueous electrolytic solution. . Thereafter, the battery container 7 is covered with a battery lid so that the positive electrode lead 9 is folded, and the gasket 10 and the battery lid are caulked and fixed on the stepped portion to complete the assembly of the lithium ion secondary battery 20. Let

  Next, examples of the lithium ion secondary battery 20 manufactured according to the present embodiment will be described. In addition, it describes together about the lithium ion secondary battery of the comparative example produced for the comparison.

Example 1
As shown in Table 1 below, in Example 1, the ratio of negative electrode discharge capacity / positive electrode discharge capacity was 1.0, initial charge capacity of graphitizable carbon was 350 mAh / g, discharge capacity of graphitizable carbon / initial charge capacity The lithium ion secondary battery 20 was fabricated with a ratio of 0.85 and a graphitized carbon discharge capacity of 0 V to 0.2 V / discharge capacity ratio of 0.2 V to 1.0 V of 0.8.

(Example 2)
As shown in Table 1, in Example 2, the negative electrode discharge capacity / positive electrode discharge capacity ratio was 1.1, the graphitized carbon 0 V to 0.2 V discharge capacity / 0.2 V to 1.0 V discharge capacity ratio. A lithium ion secondary battery 20 was produced in the same manner as in Example 1 except that the value was 1.0.

(Example 3 to Example 4)
As shown in Table 1, in Examples 3 to 4, lithium ion secondary batteries 20 were produced in the same manner as in Example 1 except that the negative electrode discharge capacity / positive electrode discharge capacity ratio was changed. That is, the negative electrode discharge capacity / positive electrode discharge capacity ratio was 1.2 in Example 3 and 1.3 in Example 4.

(Example 5)
As shown in Table 1, in Example 5, lithium ion was the same as in Example 1 except that the negative electrode discharge capacity / positive electrode discharge capacity ratio was 1.2 and the initial charge capacity of graphitizable carbon was 250 mAh / g. A secondary battery 20 was produced.

(Example 6)
As shown in Table 1, in Example 6, a lithium ion secondary battery 20 was produced in the same manner as in Example 1 except that the initial charge capacity of graphitizable carbon was 450 mAh / g.

(Example 7)
As shown in Table 1, Example 7 is the same as Example 1 except that the graphitizable carbon initial charge capacity is 230 mAh / g and the graphitizable carbon discharge capacity / initial charge capacity ratio is 0.90. Thus, a lithium ion secondary battery 20 was produced.

(Example 8)
As shown in Table 1, in Example 8, a lithium ion secondary battery 20 was produced in the same manner as in Example 1 except that the ratio of discharge capacity / initial charge capacity of graphitizable carbon was 0.80.

Example 9
As shown in Table 1, in Example 9, the ratio of the discharge capacity / initial charge capacity of graphitizable carbon is 0.90, the discharge capacity of graphitized carbon is 0V to 0.2V / 0.2V to 1.0V. A lithium ion secondary battery 20 was produced in the same manner as in Example 1 except that the discharge capacity ratio was 1.2.

(Comparative Examples 1 to 2)
As shown in Table 1, in Comparative Examples 1 and 2, lithium ion secondary batteries were produced in the same manner as in Example 1 except that the negative electrode discharge capacity / positive electrode discharge capacity ratio was changed. That is, the ratio of negative electrode discharge capacity / positive electrode discharge capacity was 0.9 in Comparative Example 1 and 1.4 in Comparative Example 2.

(Evaluation)
With respect to a plurality of each of the lithium ion secondary batteries of Examples and Comparative Examples produced as described above, the initial output and the output retention rate after the cycle test were measured, and the charge / discharge characteristics were evaluated. In the measurement of the initial output, the battery was discharged for 10 seconds at a current value of 10 A, 30 A, and 90 A from a fully charged state of 4.1 V in an atmosphere of 25 ± 2 ° C., and the battery voltage at each 5 second was measured. The battery voltage is plotted on the vertical axis against the current value on the horizontal axis, and the current value at the point where the straight line approximating the three points intersects the final voltage of 2.7 V is read, and this current value and 2.7 V The product was the output of the lithium ion secondary battery. In the cycle test, a high load current of about 50 A was applied for about 5 seconds in both the charging direction and the discharging direction in an atmosphere of 50 ± 3 ° C., and a pulse cycle test of about 30 seconds per cycle including the rest time was continuously performed. Repeated 100,000 times. The output after the cycle test was measured in the same manner as the measurement of the initial output, and the ratio of the output after the cycle test to the initial output was obtained as a percentage, and the output retention rate at 100,000 cycles was obtained. The results of the initial output and the output maintenance ratio at 100,000 cycles are shown together in Table 1.

  As shown in Table 1, in the lithium ion secondary battery of Comparative Example 1 in which the negative electrode discharge capacity / positive electrode discharge capacity ratio was 0.9, the initial output was excellent at 820 W, but the output maintenance rate at 100,000 cycles Was 65%, and sufficient cycle characteristics could not be obtained. Further, in the lithium ion secondary battery of Comparative Example 2 in which the negative electrode discharge capacity / positive electrode discharge capacity ratio was 1.4, the initial output and the output maintenance rate at 100,000 cycles were 650 W and 68%, respectively, and sufficient output characteristics and Cycle characteristics could not be obtained. On the other hand, in the lithium ion secondary batteries 20 of Examples 1 to 9 in which the negative electrode discharge capacity / positive electrode discharge capacity ratio was 1.0 or more and 1.3 or less, all of the initial outputs were 750 W or more, 10 The output retention rate at 10,000 cycles was over 80%, and the battery was excellent. Therefore, it was found that the lithium ion secondary battery 20 having excellent output and cycle characteristics can be obtained by setting the negative electrode discharge capacity / positive electrode discharge capacity ratio to 1.0 or more and 1.3 or less. In the lithium ion secondary batteries 20 of Example 3 and Example 4 in which the negative electrode discharge capacity / positive electrode discharge capacity ratios were 1.2 and 1.3, respectively, considering that a slight decrease in the initial output was recognized. It was found that the initial output and cycle characteristics can be further improved by setting the negative electrode discharge capacity / positive electrode discharge capacity ratio to 1.0 to 1.1.

  In addition, Example 6 in which the initial charge capacity of graphitizable carbon was 450 mAh / g and the discharge capacity / initial charge capacity ratio was 0.85, and the initial charge capacity was 230 mAh / g, and the discharge capacity / initial charge capacity ratio was In the lithium ion secondary battery 20 of Example 7 with 0.90, the initial output showed 800 W and 750 W, respectively, but the output retention rate at 100,000 cycles was only 80%, and the cycle characteristics were slightly A decrease was observed. Further, in the lithium ion secondary battery 20 of Example 8 in which the graphitized carbon discharge capacity / initial charge capacity ratio was 0.80, the output retention rate at 100,000 cycles was 80%, and the initial output was 750 W. There was a slight decrease in cycle characteristics and initial output. Further, the lithium of Example 9 in which the graphitized carbon has a discharge capacity ratio of 0V to 0.2V / discharge capacity ratio of 0.2V to 1.0V of 1.2 and a discharge capacity / initial charge capacity ratio of 0.90. In the ion secondary battery 20, although the initial output showed 820W, the output maintenance rate at the time of 100,000 cycles was only 83%, and the cycle characteristics were slightly reduced.

  From these results, in order to improve the output and cycle characteristics of the lithium ion secondary battery 20, the initial charge capacity is easily 250 mAh / g or more and 350 mAh / g or less, and the discharge capacity / initial charge capacity ratio is 0.85 or more. It has been found preferable to use graphitized carbon. Further, by using graphitizable carbon having a discharge capacity ratio of 0 V to 0.2 V / discharge capacity ratio of 0.2 V to 1.0 V of 1.0 or less, the output and cycle characteristics of the lithium ion secondary battery 20 are further improved. It has been found that it can be improved.

  As described above, in the lithium ion secondary battery 20 of the present embodiment, the graphitizable carbon material is used as the negative electrode active material. In the graphitizable carbon material, the irreversible capacity is smaller than that of the non-graphitizable carbon material, and since the lifetime in the constant voltage region (low potential region) is good, this region can also be used effectively. A lithium ion secondary battery optimized using a non-graphitizable carbon material and a graphitizable carbon material was prepared, and the battery capacities were compared. When the non-graphitizable carbon material was used, 6.25 Ah, graphitizable When the carbon material was used, a result of 6.92 Ah was obtained. Therefore, by using an easily graphitized carbon material for the negative electrode active material, an effect of improving the battery capacity of about 10% can be obtained.

  Moreover, in the lithium ion secondary battery 20 of this embodiment, the negative electrode discharge capacity / positive electrode discharge capacity ratio is set to 1.0 or more and 1.3 or less. For this reason, at the time of charging / discharging, it will be used to the low potential area | region of a graphitizable carbon material, a battery voltage rises from the relationship of the electrical potential difference of a positive electrode, and a battery output can be improved. Furthermore, since the low potential region of graphitizable carbon material is used, there is a general concern that the lifetime will be reduced. However, with graphitizable carbon material, expansion and contraction during charge / discharge in the low potential region is reduced. Deterioration can be suppressed and life characteristics can be improved. Moreover, since a high potential of the positive electrode plate can be suppressed when a constant battery voltage is obtained by using the low potential region, further improvement in life can be expected.

  Further, in the lithium ion secondary battery 20 of the present embodiment, a graphitizable carbon material having an initial charge capacity of 250 mAh / g or more and 350 mAh / g or less and a discharge capacity / initial charge capacity ratio of 0.85 or more is used. . Thereby, since the use electric potential area | region of an easily graphitized carbon material is optimized, it can be set as the lithium ion secondary battery which was further excellent in cycling characteristics with high output.

  Furthermore, in the lithium ion secondary battery 20 of the present embodiment, a graphitizable carbon material having a discharge capacity ratio of 0 V to 0.2 V / 0.2 V to 1.0 V and a discharge capacity ratio of 1.0 or less is used. Yes. As a result, side reactions such as decomposition of the non-aqueous electrolyte in the negative electrode can be suppressed, so that a battery having further excellent cycle characteristics can be realized.

  In the present embodiment, the cylindrical lithium ion secondary battery 20 is illustrated, but the present invention is not limited to the battery shape, and can be applied to a rectangular or other polygonal lithium ion secondary battery. is there. The battery structure to which the present invention can be applied may be other than a structure in which the battery container is sealed by caulking and fixing the battery lid. As an example of such a structure, a structure in which the positive and negative external terminals pass through the battery lid and the positive and negative external terminals are pressed against each other through the shaft core in the battery container can be exemplified. Furthermore, in the present embodiment, a wound structure having an electrode group in which a positive electrode plate and a negative electrode plate are wound is illustrated, but the present invention is not limited to this, and lithium ions having a stacked structure are used. It is applicable also to a secondary battery.

  In this embodiment, lithium manganate is exemplified as the positive electrode active material, but the present invention is not limited to this. The positive electrode active material that can be used in other embodiments is a material capable of inserting / extracting lithium ions, and may be any lithium transition metal composite oxide in which a sufficient amount of lithium ions has been inserted in advance. A material obtained by substituting or doping a part of lithium or transition metal therein with other elements may be used. Furthermore, there is no restriction | limiting in particular also about crystal structure, For example, materials, such as a spinel structure and a layered structure, can be used.

  Furthermore, in this embodiment, although the electrically conductive material and the binder were illustrated, this invention is not limited to these electrically conductive materials and a binder, Any thing normally used for a lithium ion secondary battery can be used. . As binders that can be used other than the present embodiment, polytetrafluoroethylene (PTFE), polyethylene, polystyrene, polybutadiene, butyl rubber, nitrile rubber, styrene / butadiene rubber, polysulfide rubber, nitrocellulose, cyanoethyl cellulose, various latexes, Examples thereof include polymers such as acrylonitrile, vinyl fluoride, vinylidene fluoride, propylene fluoride, chloroprene fluoride, and mixtures thereof.

Furthermore, in the present embodiment, a nonaqueous electrolytic solution in which LiPF ₆ is dissolved in a mixed solvent in which ethylene carbonate, dimethyl carbonate, and diethyl carbonate are mixed at a volume ratio of 1: 1: 1 is exemplified. A nonaqueous electrolytic solution obtained by dissolving the above in an organic solvent may be used, and the present invention is not particularly limited to the lithium salt or organic solvent used. For example, examples of the electrolyte include LiClO ₄ , LiAsF ₆ , LiBF ₄ , LiB (C ₆ H ₅ ) ₄ , CH ₃ SO ₃ Li, CF ₃ SO ₃ Li, and a mixture thereof. Examples of the organic solvent include propylene carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, Examples include sulfolane, methyl sulfolane, acetonitrile, propionitrile, and a mixed solvent in which two or more of these are mixed. Furthermore, the mixing ratio is not limited.

  Since the present invention provides a lithium ion secondary battery that can suppress a decrease in battery output and improve life characteristics, and contributes to the manufacture and sale of lithium ion secondary batteries, it has industrial applicability. .

It is sectional drawing of the cylindrical lithium ion secondary battery of embodiment to which this invention is applied.

Explanation of symbols

6 Electrode group 20 Cylindrical lithium ion secondary battery (lithium ion secondary battery)
W1 positive plate (positive electrode)
W2 Cathode active material mixture (active material mixture)
W3 Negative electrode plate (negative electrode)
W4 Negative electrode active material mixture (active material mixture)

Claims (3)

  A positive electrode in which an active material mixture containing a lithium transition metal composite oxide as a positive electrode active material is applied to the positive electrode current collector; and a negative electrode in which an active material mixture containing a negative electrode active material is applied to the negative electrode current collector; In the lithium ion secondary battery having the above, an easily graphitizable carbon material is used as the negative electrode active material, and the ratio of the discharge capacity of the negative electrode to the discharge capacity of the positive electrode after the initial charge is 1.0 or more and 1. A lithium ion secondary battery characterized by being 3 or less.   The said graphitizable carbon material has an initial charge capacity of 250 mAh / g or more and 350 mAh / g or less, and a ratio of a discharge capacity to the initial charge capacity of 0.85 or more. Lithium ion secondary battery.   The ratio of the discharge capacity of 0V to 0.2V to the discharge capacity of 0.2V to 1.0V in the graphitizable carbon material is 1.0 or less. Lithium ion secondary battery.

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