JP5284933B2 - Lithium secondary battery and manufacturing method thereof - Google Patents

Description

  The present invention relates to a lithium secondary battery and a method for manufacturing the same.

  Conventionally, in the field of rechargeable secondary batteries, aqueous batteries such as lead batteries, nickel-cadmium batteries, and nickel-hydrogen batteries have been mainstream.

  On the other hand, due to the problems of global warming and fuel depletion, electric vehicles that are driven only by electric motors and hybrid electric vehicles that are partly driven by electric motors are attracting attention. Large and high input / output characteristics have been demanded. As a power source that meets such requirements, a lithium secondary battery having a high voltage has attracted attention.

  Generally, a lithium secondary battery has a positive electrode active material mixture containing a lithium-containing metal oxide capable of reversibly occluding and releasing lithium ions and a negative electrode active material mixture containing a carbon material uniformly on both sides of the electrode substrate. It is configured as a battery by coating and laminating or winding through a separator such as a microporous membrane so that they are not short-circuited.

  Negative electrode materials include non-graphitizable carbon materials for increasing the amount of lithium ion occlusion (capacity) between layers of negative electrode carbon, and high crystallinity with developed crystal structures that can be designed to high energy density Graphite, which is a carbon material, is used.

  Patent Document 1 discloses a two-layer technology in which a first layer containing a graphite material is provided on a negative electrode conductive substrate, and a second layer containing a non-graphitizable carbon material is provided on the first layer. Is disclosed.

  Patent Document 2 discloses a technique in which an active material is scattered in the form of dots on the surface of a current collector of an electrode.

JP 2008-59999 A Japanese Patent Laying-Open No. 2005-050681

  An object of the present invention is to maintain the reliability of the lithium secondary battery and increase the capacity.

  The lithium secondary battery of the present invention is an electrode group formed by winding a positive electrode that occludes and releases lithium, a negative electrode that occludes and releases lithium, and a separator sandwiched between the positive electrode and the negative electrode around an axis. In which the first negative electrode active material layer is formed on the surface of the negative electrode current collector, and the second negative electrode active material is formed on the first negative electrode active material layer. A layer is formed, and the second negative electrode active material layer has a larger volume change rate than the first negative electrode active material layer.

  ADVANTAGE OF THE INVENTION According to this invention, the deformation | transformation by expansion | swelling of a negative electrode can be prevented, and a lithium secondary battery with high reliability and a large capacity can be provided.

It is a perspective view which shows the electrode for lithium secondary batteries of an Example. It is a perspective view which shows the electrode group incorporated in the lithium secondary battery of an Example. It is a partial expanded sectional view which shows the fine structure of the electrode group in the area | region R of FIG. 2A. It is a front view which shows the internal state of the lithium secondary battery of an Example. It is a graph which shows the relationship between the coating area ratio of the active material layer in the lithium secondary battery of an Example, and the thickness increase rate of an electrode. It is a graph which shows the relationship between the coating area ratio of the active material layer in the lithium secondary battery of an Example, and a discharge capacity ratio.

  The present invention relates to a lithium secondary battery, and more particularly to the configuration of the negative electrode.

  Hereinafter, the lithium secondary battery which is an embodiment of the present invention, a negative electrode used therefor, and a manufacturing method thereof will be described.

  This embodiment is basically configured as follows.

  The lithium secondary battery includes a positive electrode that occludes and releases lithium, a negative electrode that occludes and releases lithium, and a lithium electrode that incorporates an electrode group formed by winding a separator sandwiched between the positive electrode and the negative electrode around an axis. In the secondary battery, the negative electrode is formed by forming a first negative electrode active material layer on the surface of the negative electrode current collector and forming a second negative electrode active material layer on the first negative electrode active material layer. The second negative electrode active material layer has a larger volume change rate than the first negative electrode active material layer, and is between the separator and the first negative electrode active material layer in contact with the negative electrode inside the electrode group. Forms a second negative electrode active material layer and a gap.

  In the lithium secondary battery, the discharge capacity per unit volume of the second negative electrode active material layer is preferably larger than that of the first negative electrode active material layer.

  In the lithium secondary battery, the volume of the first negative electrode active material layer is preferably larger than that of the second negative electrode active material layer.

  In the lithium secondary battery, it is preferable that the second negative electrode active material layer is formed in a dot shape, a lattice shape, a vertical stripe shape, or a horizontal stripe shape.

  The lithium secondary battery preferably has a higher output per unit volume of the first negative electrode active material layer than that of the second negative electrode active material layer.

  In the lithium secondary battery, it is desirable that the first negative electrode active material layer includes a non-graphitizable carbon material.

  In the lithium secondary battery, it is preferable that the second negative electrode active material layer includes a highly crystalline carbon material.

  In the negative electrode, a first negative electrode active material layer is formed on a surface of a negative electrode current collector, a second negative electrode active material layer is formed on the first negative electrode active material layer, and a second negative electrode active material layer is formed. Reduces the coating area compared to the first negative electrode active material layer.

  The negative electrode preferably has a coating area ratio of the second negative electrode active material layer to the first negative electrode active material layer of 50 to 80%.

  The other structure of the negative electrode is the same as the detailed structure of the lithium secondary battery.

  The method for manufacturing a lithium secondary battery includes a step of forming a first negative electrode active material layer on a surface of a negative electrode current collector constituting a negative electrode, and a second negative electrode active material on the first negative electrode active material layer. Forming a layer, and forming a gap between the second negative electrode active material layers.

  The method for producing the lithium secondary battery includes: a second negative electrode active material layer including a screen printing method, an inkjet method, a spray method, a gravure printing method, a thermal transfer method, a relief printing method, an intaglio printing method, and an offset printing method. It is desirable to form by using any one type or a combination of two or more types.

  The negative electrode manufacturing method includes a step of forming a first negative electrode active material layer on a surface of a negative electrode current collector, and a step of forming a second negative electrode active material layer on the first negative electrode active material layer. The second negative electrode active material layer has a coating area narrower than that of the first negative electrode active material layer.

  Hereinafter, the lithium secondary battery of the present embodiment will be described with reference to the drawings.

  FIG. 2A illustrates an electrode group built in the lithium secondary battery of this embodiment.

  The lithium secondary battery shown in this figure is flat, and the electrode group 5 is housed in a flat battery container (not shown).

  The electrode group 5 is obtained by winding a strip-like negative electrode 6 and a positive electrode 8 around an axis 11 via separators 10a and 10b. Around the shaft core 11, a separator 10a, a negative electrode 6, a separator 10b, and a positive electrode 8, which are insulating members, are wound in a stacked state.

  The positive electrode 8 is provided with a plurality of positive electrode lead pieces 9 of a positive electrode base material foil (positive electrode current collector). The negative electrode 6 is provided with a plurality of negative electrode lead pieces 7 of a negative electrode base foil (negative electrode current collector).

  In addition, the area | region R in a figure shows the part of the negative electrode 6 and the separator 10 which were laminated | stacked in the electrode group.

  FIG. 2B is a partial enlarged cross-sectional view showing the fine structure of the electrode group in the region R of FIG. 2A, and shows a partial three-dimensional shape of the laminated negative electrode 6 and separator 10.

  Inside the electrode group, the negative electrode 6 is in contact with the separator 10. The negative electrode 6 has a structure in which a negative electrode current collector 20, a first negative electrode active material layer 21 and a second negative electrode active material layer 22 are laminated, and the area of the second negative electrode active material layer 22 is It is narrower than the area of one negative electrode active material layer 21. For this reason, the second negative electrode active material layer 22 and the gap 31 are formed between the separator 10 and the first negative electrode active material layer 21.

  Due to the presence of the gap 31, the second negative electrode active material layer 22 extends into the gap 31 even when the second negative electrode active material layer 22 undergoes volume expansion. That is, the gap 31 can absorb the volume expansion of the second negative electrode active material layer 22. Thereby, the increase in the thickness of the negative electrode 6 can be suppressed.

  As a result, expansion of the electrode group can be suppressed, and deformation due to expansion of the negative electrode can be prevented.

  Hereinafter, the positive electrode 8 and the negative electrode 6 will be described in detail.

(Positive electrode)
The positive electrode 8 is obtained by forming a positive electrode active material layer on the surface of a positive electrode current collector. A positive electrode active material layer contains a positive electrode active material and a binder, and may mix a electrically conductive agent with these as needed. The positive electrode active material layer is formed by applying (applying) a positive electrode mixture to the surface of the positive electrode current collector and drying it. The positive electrode mixture is applied to both surfaces of the positive electrode current collector substantially evenly (with a uniform thickness). Here, performing coating and drying is called coating.

  The positive electrode mixture is prepared by mixing a positive electrode active material, a binder, a dispersion solvent, and, if necessary, a conductive agent.

  In this embodiment, lithium manganate, which is a lithium transition metal oxide, is used as the positive electrode active material. The positive electrode current collector is an aluminum foil.

  As the positive electrode mixture, for example, 10 parts by weight of flaky graphite as a conductive agent and polyvinylidene fluoride as a binder (binder) (hereinafter abbreviated as PVDF) 5 with respect to 100 parts by weight of lithium manganate. What mix | blended the weight part is used. This positive electrode mixture is mixed with N-methylpyrrolidone (hereinafter abbreviated as NMP) as a dispersion solvent to adjust the viscosity. The positive electrode mixture with adjusted viscosity is applied (applied) to a 20 μm-thick aluminum foil, which is a positive electrode current collector, and dried to obtain a positive electrode.

  This positive electrode has at least one end portion where a positive electrode active material layer formed continuously in the longitudinal direction of the positive electrode current collector (aluminum foil) is not applied.

  Thereafter, this positive electrode is pressed to produce a positive electrode tab (positive electrode lead piece) that is cut out in a rectangular shape, leaving a portion not coated with the positive electrode active material layer with a width of several millimeters.

(Negative electrode)
The negative electrode 6 is obtained by forming a negative electrode active material layer on the surface of a negative electrode current collector. A negative electrode active material layer contains a negative electrode active material and a binder, and may mix a electrically conductive agent with these as needed. The negative electrode active material layer is formed by applying (coating) a negative electrode mixture to the surface of the negative electrode current collector and drying it.

  The negative electrode mixture is prepared by mixing a negative electrode active material, a binder, a dispersion solvent, and, if necessary, a conductive agent.

  In the present embodiment, two negative electrode active material layers are stacked.

  FIG. 1 is a perspective view showing an electrode for a lithium secondary battery according to an embodiment of the present invention.

  In this figure, first, the first negative electrode active material layer 21 is formed on the surface (both sides) of the negative electrode current collector 20 by coating the first negative electrode active material layer 21 substantially uniformly, and the second negative electrode active material layer 22 is formed thereon in the form of dots. It is formed so as to be scattered.

  As the first negative electrode active material layer 21, a material having a small volume change rate associated with charge / discharge is used, and as the second negative electrode active material layer 22, a material having a large volume change rate associated with charge / discharge is used.

  The negative electrode 6 has at least one end 23 at which a negative electrode active material layer formed continuously in the longitudinal direction of the negative electrode current collector 20 is not applied.

  Thereafter, the negative electrode is pressed to produce a negative electrode tab (negative electrode lead piece) that is cut out in a rectangular shape, leaving a portion not coated with the negative electrode active material layer with a width of several millimeters.

  The material constituting the second negative electrode active material layer 22 preferably has a larger discharge capacity per unit volume than the material constituting the first negative electrode active material layer 21.

  It is desirable that the material constituting the first negative electrode active material layer 21 has a higher output per unit volume than the material constituting the second negative electrode active material layer 22.

  As the negative electrode active material used for the first negative electrode active material layer 21, it is desirable to use a non-graphitizable carbon material. A non-graphitizable carbon material is a substance that does not become graphite when heated in an inert atmosphere. Fine graphite crystals are randomly arranged, and a space of several nanometers is placed between the crystals. It has a hole. Due to the presence of these vacancies, the volume change rate due to insertion and extraction of lithium is small.

  The second negative electrode active material layer 22 is desirably made of graphite that is a highly crystalline carbon material. Graphite has relatively large crystal particles and few vacancies. For this reason, the volume change rate by occlusion and release of lithium is relatively large.

  The negative electrode current collector 20 is preferably made of rolled copper foil.

  Graphite has a larger discharge capacity per unit volume than non-graphitizable carbon materials. Moreover, the non-graphitizable carbon material has a higher output per unit volume than graphites.

  As the negative electrode mixture, for example, a mixture of 90 parts by weight of the non-graphitizable carbon material and 10 parts by weight of PVDF as a binder is used. NMP is mixed with this negative electrode mixture as a dispersion solvent to adjust the viscosity. The negative electrode mixture with adjusted viscosity is applied (coated) to a rolled copper foil having a thickness of 10 μm, which is a negative electrode current collector, and dried.

  The second negative electrode active material layer 22 is formed so as to be interspersed with a gap on the first negative electrode active material layer 21. When the second negative electrode active material layers 22 are interspersed in dots, it is desirable that the adjacent second negative electrode active material layers 22 do not contact each other. The area occupied by the second negative electrode active material layer 22 is desirably 50 to 80% of the area of the negative electrode current collector 20 where the first negative electrode active material layer 21 is applied.

  When the occupied area of the second negative electrode active material layer 22 is greater than 80% of the area where the first negative electrode active material layer 21 is applied, the amount of expansion deformation in the height direction of the second negative electrode active material layer 22 is increased. Since it becomes large, the cycling characteristics of a battery will fall. Further, when the occupied area of the second negative electrode active material layer 22 is smaller than 50% of the area where the first negative electrode active material layer 21 is applied, the effect of increasing the capacity is reduced.

  As a method for forming the second active material layer 22 on the first negative electrode active material layer 21, a screen printing method, an ink jet method, a spray method, a gravure printing method, a thermal transfer method, a relief printing method, an intaglio printing method, and Any one or a combination of two or more offset printing methods can be used.

(Production of battery)
Using the positive electrode and the negative electrode produced by the above method, the electrode group is produced by winding around a shaft core through a polyethylene separator so that these two electrodes do not directly contact each other.

  FIG. 3 is a front view showing the internal state of the lithium secondary battery of the present embodiment.

  The lithium secondary battery shown in this figure has an electrode group 5 housed in an aluminum battery case 1 (battery can), and is sealed by welding the battery case 1.

  The electrode group 5 is wound in a state where the separator 10a, the negative electrode 6, the separator 10b, the positive electrode 8, and the separator 10c, which are insulating members, are laminated.

  The positive electrode 8 is provided with a plurality of positive electrode lead pieces 9 of a positive electrode base material foil (positive electrode current collector). The negative electrode 6 is provided with a plurality of negative electrode lead pieces 7 of a negative electrode base foil (negative electrode current collector). The negative electrode lead piece 7 is connected to the negative electrode current collector plate 101, and the positive electrode lead piece 9 is connected to the positive electrode current collector plate 102. The negative current collector 101 is connected to the negative external terminal 103, and the positive current collector 102 is connected to the positive external terminal 104.

  The battery lid of the battery container 1 is provided with a liquid injection port (not shown). The electrolytic solution is injected from the liquid injection port, and the liquid injection port is closed and sealed.

As the electrolytic solution, an organic electrolytic solution (nonaqueous electrolytic solution) in which 1 mol / L (mol / liter) LiPF ₆ is dissolved after EC, DMC, and EMC are mixed at a volume ratio of 1: 1: 1 is used. .

  Next, examples of the lithium secondary battery produced by the above method will be described. A conventional lithium secondary battery manufactured as a comparative example is also described. In the following examples and comparative examples, the manufacturing method of the positive electrode and the battery is the same, so only the manufacturing method of the negative electrode will be described.

  An electrode in which a first negative electrode active material layer was formed on the surface of the negative electrode current collector and a second negative electrode active material layer was formed on the first negative electrode active material layer was produced. The application area of the second negative electrode active material layer was 80% with respect to the application area of the first negative electrode active material. The coating pattern of the second negative electrode active material layer was dot-shaped.

  An electrode in which a first negative electrode active material layer was formed on the surface of the negative electrode current collector and a second negative electrode active material layer was formed on the first negative electrode active material layer was produced. The application area of the second negative electrode active material layer was 50% with respect to the application area of the first negative electrode active material. The coating pattern of the second negative electrode active material layer was dot-shaped.

(Comparative Example 1)
An electrode having a first negative electrode active material layer formed on the surface of the negative electrode current collector was produced. The second negative electrode active material layer was not coated.

(Comparative Example 2)
An electrode in which a first negative electrode active material layer was formed on the surface of the negative electrode current collector and a second negative electrode active material layer was formed on the first negative electrode active material layer was produced. The application area of the second negative electrode active material layer was 100% with respect to the application area of the first negative electrode active material.

  Using the lithium secondary batteries of Examples 1 and 2 and Comparative Examples 1 and 2, the charge / discharge test and the standing test were performed.

  In the charge / discharge test, the current value was set to 1C, and after charging at constant current and constant voltage to 4.2V, charge / discharge to discharge to 3.0V was performed for 5 cycles.

  In the standing test, the battery was left for 30 days in a charged state at a temperature of 50 ° C. and 4.1 V. The thickness of the battery before and after the standing test was measured.

  Table 1 shows the results of the charge / discharge test and the standing test.

  From Table 1, it can be seen that the discharge capacity at the fifth charge / discharge cycle increased by 10% or more with respect to Comparative Example 1 in the case of Examples 1 and 2.

  In Examples 1 and 2, the charge / discharge efficiency in the initial charge was 80% or more. On the other hand, in Comparative Example 1, the charge / discharge efficiency in the initial charge was 75%.

  Further, the rate of increase in the thickness of the battery after the standing test is 6.0% in Comparative Example 2, which is larger than those in Examples 1 and 2 (2.5% or less). From this result, it is considered that Comparative Example 2 is inferior to Examples 1 and 2 in terms of reliability in repeated charge / discharge.

  From these test results, the lithium secondary batteries of Examples 1 and 2 can alleviate the expansion of the electrodes during charging and discharging.

  4 and 5 are graphs of the results shown in Table 1. FIG.

  FIG. 4 relates to the rate of increase in battery thickness. The horizontal axis represents the ratio of the area where the second negative electrode active material layer is applied to the area where the first negative electrode active material layer is applied (the ratio of the coating area of the second negative electrode active material layer to the first negative electrode active material layer). The vertical axis represents the rate of increase in the thickness of the battery before and after the standing test.

  It can be seen that when the coating area ratio exceeds 80%, the rate of increase in battery thickness increases rapidly. Therefore, the coating area ratio is desirably 80% or less.

  FIG. 5 relates to the discharge capacity. The horizontal axis represents the coating area ratio, and the vertical axis represents the discharge capacity at the fifth cycle (referred to as the discharge capacity ratio). The discharge capacity ratio is calculated based on the case where the coating area ratio is 0% (the case where there is no second negative electrode active material layer).

  When the coating area ratio is less than 50%, the effect of improving the discharge capacity is reduced. Therefore, the coating area ratio is desirably 50% or more.

  In the above-described embodiments, the coating pattern of the second negative electrode active material layer is a dot shape, but the coating pattern is not limited to this, and may be a lattice shape, a vertical stripe shape, or a horizontal stripe shape. . The coating pattern of the second negative electrode active material layer only needs to be formed with a gap. Here, the gap is not a gap between the contact surfaces of the first negative electrode active material layer and the second negative electrode active material layer, but that the second negative electrode active material layers are formed with a gap between them. Say. From the viewpoint of electron and ion mobility, it is desirable that there is no gap in the contact surface between the first negative electrode active material layer and the second negative electrode active material layer.

  1: battery container, 5: electrode group, 6: negative electrode, 7: negative electrode lead piece, 8: positive electrode, 9: positive electrode lead piece, 10a, 10b, 10c: separator, 11: shaft core, 20: negative electrode current collector, 21: first negative electrode active material layer, 22: second negative electrode active material layer, 31: gap.

Claims (14)

A lithium secondary battery incorporating an electrode group formed by winding a positive electrode that occludes and releases lithium, a negative electrode that occludes and releases lithium, and a separator sandwiched between the positive electrode and the negative electrode around an axis. The negative electrode is obtained by forming a first negative electrode active material layer on a surface of a negative electrode current collector and forming a second negative electrode active material layer on the first negative electrode active material layer, The second negative electrode active material layer has a larger volume change rate due to insertion and extraction of lithium than the first negative electrode active material layer, and the separator in contact with the negative electrode inside the electrode group and the first negative electrode active material layer. between the anode active material layer, the second have a negative electrode active material layer and the gap, the second negative electrode active material layer, the discharge per unit volume than that of the first negative electrode active material layer The first negative electrode active material layer has a larger capacity than the second negative electrode active material layer. The second negative electrode active material layer is formed in a dot shape, a lattice shape, a vertical stripe shape, or a horizontal stripe shape, and the first negative electrode active material layer is the second negative electrode active material layer. The lithium secondary battery is characterized in that the output per unit volume is higher than that of the first negative electrode active material layer, and the first negative electrode active material layer contains a non-graphitizable carbon material . The second negative electrode active material layer, lithium secondary battery according to claim 1, characterized in that it comprises a highly crystalline carbon material. A first negative electrode active material layer is formed on the surface of the negative electrode current collector, a second negative electrode active material layer is formed on the first negative electrode active material layer, and the second negative electrode active material layer includes: The coating area is narrower than that of the first negative electrode active material layer, and the second negative electrode active material layer has a volume change rate due to insertion and extraction of lithium as compared with the first negative electrode active material layer. rather large, the first large discharge capacity of per unit volume than the negative electrode active material layer, the first anode active material layer is larger volume than that of the second negative electrode active material layer, the second The negative electrode active material layer 2 is formed in a dot shape, a lattice shape, a vertical stripe shape, or a horizontal stripe shape, and the first negative electrode active material layer has a volume per unit volume as compared with the second negative electrode active material layer. output is high, the first negative electrode active material layer, negative for a lithium secondary battery which comprises a non-graphitizable carbon material . 4. The negative electrode for a lithium secondary battery according to claim 3, wherein a coating area ratio of the second negative electrode active material layer to the first negative electrode active material layer is 50 to 80%. The second negative electrode active material layer, the first negative electrode for lithium secondary battery according to claim 3 or 4, wherein the discharge capacity per unit volume is larger than the negative electrode active material layer. The negative electrode for a lithium secondary battery according to any one of claims 3 to 5 , wherein the first negative electrode active material layer has a larger volume than the second negative electrode active material layer. The second negative electrode active material layer, a dot-like, grid-like, for a lithium secondary battery according to any one of claims 3-6, characterized in that it is formed in vertical stripes or horizontal stripes Negative electrode. The lithium secondary battery according to any one of claims 3 to 7 , wherein the first negative electrode active material layer has a higher output per unit volume than the second negative electrode active material layer. the negative electrode of the use. The negative electrode for a lithium secondary battery according to any one of claims 3 to 8 , wherein the first negative electrode active material layer includes a non-graphitizable carbon material. The negative electrode for a lithium secondary battery according to any one of claims 3 to 9 , wherein the second negative electrode active material layer includes a highly crystalline carbon material. Manufacture of a lithium secondary battery having a built-in electrode group formed by winding a positive electrode that occludes and releases lithium, a negative electrode that occludes and releases lithium, and a separator sandwiched between the positive electrode and the negative electrode. A method comprising: forming a first negative electrode active material layer on a surface of a negative electrode current collector constituting the negative electrode; and forming a second negative electrode active material layer on the first negative electrode active material layer And forming the second negative electrode active material layer and a gap between the separator in contact with the negative electrode inside the electrode group and the first negative electrode active material layer , The second negative electrode active material layer has a larger volume change rate due to insertion and extraction of lithium than the first negative electrode active material layer, and has a discharge capacity per unit volume as compared with the first negative electrode active material layer. The first negative electrode active material layer is larger than the second negative electrode active material layer. The second negative electrode active material layer is formed in a dot shape, a lattice shape, a vertical stripe shape, or a horizontal stripe shape, and the first negative electrode active material layer is formed of the second negative electrode active material. The method for producing a lithium secondary battery , wherein the output per unit volume is higher than that of the layer, and the first negative electrode active material layer contains a non-graphitizable carbon material . The second negative electrode active material layer may be any one or more of a screen printing method, an ink jet method, a spray method, a gravure printing method, a thermal transfer method, a relief printing method, an intaglio printing method, and an offset printing method. The method for producing a lithium secondary battery according to claim 11, wherein the method is formed by using in combination. A step of forming a first negative electrode active material layer on the surface of the negative electrode current collector, and a step of forming a second negative electrode active material layer on the first negative electrode active material layer. The negative electrode active material layer has a coating area smaller than that of the first negative electrode active material layer, and a volume change rate due to insertion and extraction of lithium is larger than that of the first negative electrode active material layer. The negative electrode active material layer 2 has a larger discharge capacity per unit volume than the first negative electrode active material layer, and the first negative electrode active material layer has a volume higher than that of the second negative electrode active material layer. The second negative electrode active material layer is formed in a dot shape, a lattice shape, a vertical stripe shape, or a horizontal stripe shape, and the first negative electrode active material layer is compared with the second negative electrode active material layer. output per unit volume Te is high, the first negative electrode active material layer, characterized in that it comprises a non-graphitizable carbon material lithium Method of manufacturing an anode for a beam rechargeable battery. The second negative electrode active material layer may be any one or more of a screen printing method, an ink jet method, a spray method, a gravure printing method, a thermal transfer method, a relief printing method, an intaglio printing method, and an offset printing method. The method for producing a negative electrode for a lithium secondary battery according to claim 13 , wherein the negative electrode is formed by using in combination.

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