JP2008135376A - Electrode plate for battery and lithium secondary battery including the same - Google Patents

Electrode plate for battery and lithium secondary battery including the same Download PDF

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JP2008135376A
JP2008135376A JP2007271580A JP2007271580A JP2008135376A JP 2008135376 A JP2008135376 A JP 2008135376A JP 2007271580 A JP2007271580 A JP 2007271580A JP 2007271580 A JP2007271580 A JP 2007271580A JP 2008135376 A JP2008135376 A JP 2008135376A
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active material
current collector
protrusion
electrode plate
negative electrode
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Japanese (ja)
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Yasutaka Furuyui
Kazuyoshi Honda
康隆 古結
和義 本田
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Matsushita Electric Ind Co Ltd
松下電器産業株式会社
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Priority to JP2007271580A priority patent/JP2008135376A/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Abstract

An electrode that provides a lithium secondary battery with excellent cycle characteristics even when an active material having a large volume change during charge and discharge is used, and a lithium secondary battery using the electrode.
An electrode plate for a battery according to the present invention includes a current collector including a base material and a plurality of protrusions supported on the base material, and an active material layer supported on the current collector. Prepare. The protrusion includes a conductive material that is more easily plastically deformed than the base material. The present invention also provides a lithium secondary battery using the electrode plate.
[Selection] Figure 1

Description

  The present invention relates to an improvement of an electrode plate for a battery, and further relates to a lithium secondary battery using the electrode plate.

  In recent years, with the development of portable devices such as personal computers and mobile phones, the demand for batteries as power sources has increased. A battery for use as described above is required to be used at room temperature, and at the same time, a high energy density and excellent cycle characteristics are required.

  Since a very high capacity can be obtained in response to the above demand, a battery using a material containing silicon (Si) or tin (Sn) as a negative electrode active material is promising. Examples of the material containing Si or Sn include a simple substance of Si or Sn, an oxide of Si or Sn, and an alloy containing Si or Sn.

  However, the material as described above changes its crystal structure when lithium is occluded, and its volume greatly increases. That is, the material has a large volume change during charge and discharge. For this reason, when charging / discharging is repeated, poor contact between the active material and the current collector occurs, and the charge / discharge cycle life is shortened.

In order to solve such a problem, for example, Patent Document 1 proposes forming a silicon thin film on a current collector having a roughened surface.
International Publication No. 01/029912 Pamphlet

  However, in the technique disclosed in Document 1, the Si thin film has no space inside, and the current collector is made of a single composition copper foil. For this reason, a great amount of stress generated during expansion of the active material propagates to the current collector, and the Si thin film is peeled off at the interface with the current collector, or the electrode plate is deformed.

  The electrode plate for a battery according to the present invention includes a current collector including a base material and a plurality of protrusions supported on the base material, and an active material layer supported on the current collector. The conductive material is more easily plastically deformed than the base material. The bottom of the protrusion is joined to the substrate.

  The height of the protrusion is preferably 1 to 15 μm. It is preferable that the protrusion includes copper having a purity of 99.9% by weight or more. The protrusion is preferably formed by a plating method, a vapor deposition method, a sputtering method, or a sintering method.

  The substrate preferably contains at least one selected from the group consisting of nickel foil, stainless steel foil, and copper foil. The copper foil used as the substrate preferably contains at least one element selected from the group consisting of Ni, Si, Sn, Be, Co, Ti, Fe and Zr.

  It is preferable that the active material layer includes a plurality of columnar particles, and the columnar particles are supported on the protrusions.

  At least a part of the columnar particles is preferably inclined with respect to the normal direction of the surface of the current collector. In addition, although the surface of a collector has a projection part, since it is flat according to visual observation, the normal line direction of a collector is defined uniquely.

  The columnar particles preferably include a laminate of a plurality of particle layers, and the plurality of particle layers are inclined with respect to the normal direction of the surface of the current collector. More preferably, the growth direction of the plurality of grain layers is alternately inclined in the first direction and the second direction with respect to the normal direction of the surface of the current collector.

  The present invention also provides a lithium secondary battery comprising a positive electrode capable of inserting and extracting lithium ions, the electrode plate as a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte having lithium ion conductivity. Next battery.

According to the present invention, the current collector includes a base material and a plurality of protrusions carried thereon, and the protrusion includes a conductive material that is more easily plastically deformed than the base material. The stress at the time can be absorbed by the protrusion. For this reason, the cycle characteristics of the lithium secondary battery can be improved.
By forming the active material layer from a plurality of columnar particles, the porosity of the active material layer can be increased. Therefore, the stress due to the expansion of the active material can be relaxed, and the cycle characteristics of the lithium secondary battery can be further improved.

FIG. 1 schematically shows an electrode plate 1 according to an embodiment of the present invention. FIG. 2 schematically shows the current collector 10 included in the electrode plate 1.
The battery electrode plate 1 of the present invention includes a current collector 10 including a base material 11 and a plurality of protrusions 12 directly supported thereon, and an active material layer 20 supported on the current collector. The protrusion 12 includes a conductive material that is more easily plastically deformed than the base material 11. That is, the protrusion 12 is made of a conductive material that can easily follow the expansion of the active material layer as compared with the base material 11.

  When the active material expands and contracts, a great amount of stress is generated at the interface between the active material and the current collector. Since the current collector includes protrusions that are more easily plastically deformed than the base material, the stress during expansion and contraction of the active material is absorbed by the protrusions without being concentrated at the interface between the current collector and the active material. The At this time, the amount of plastic deformation of the protrusion is about 1%, but the protrusion can disperse the stress generated at the interface between the active material and the current collector. For this reason, deformation of the electrode plate and peeling of the active material from the current collector can be suppressed.

  Furthermore, when the active material expands during the first charge, the protrusion easily plastically deforms, so that the protrusion can follow the expansion of the active material. For this reason, the stress does not propagate to the substrate. Further, the base material is less likely to be plastically deformed than the protrusions. Therefore, it is possible to suppress the generation of wrinkles on the electrode plate.

  As described above, when the current collector includes the base material and the protrusion including the conductive material that is more easily plastically deformed than the base material, the cycle characteristics of the battery can be improved.

  In addition, the expansion stress of the active material is maximum especially at the first charge. At this time, it is considered that the protrusion hardly deforms due to expansion and contraction of the active material after the protrusion is plastically deformed. This is because, during the first charge, the lithium diffusion path is secured and the element arrangement of the active material is optimized, so that stress during expansion and contraction of the active material is considered to be reduced.

  In order to follow the expansion of the active material layer, it is preferable that at least the surface layer portion of the protrusion 12 is easily plastically deformed.

  The ease with which the protrusion 12 follows the expansion of the active material layer 20 can be expressed by the hardness of the protrusion 12. For example, the hardness of the protrusion 12 can be measured by a Vickers hardness measurement method. The Vickers hardness of the protrusion 12 is desirably 100 or less, and more desirably 90 or less. Vickers hardness can be measured according to JIS Z2244.

  Even if the initial Vickers hardness of the protrusion (Vickers hardness of the protrusion immediately after production) is 130 or more, if the annealing temperature of the protrusion is lower than the annealing temperature of the base material, By performing heat treatment at a temperature at which only the protrusions are annealed, the Vickers hardness of only the protrusions can be reduced to 100 or less, for example.

The active material layer 20 supported on the current collector includes a plurality of columnar particles 21, and the columnar particles 21 are preferably supported on the protrusions 12.
By supporting the columnar particles 21 on the protrusions 12, voids can be formed in the active material layer 20. That is, the porosity of the active material layer 20 can be increased. As a result, since the expansion of the columnar particles 21 can be reduced, it is possible to further suppress the separation of the columnar particles 21 from the current collector 10 and the deformation of the electrode plate.

  Since the columnar particles 21 have a high capacity, it is preferable to include a silicon-containing material. Such a material has a large volume change at the time of charging / discharging. By using the current collector 10 as described above, even when a silicon-containing material is used, deformation of the electrode plate, active material from the current collector It is possible to sufficiently suppress the peeling and the like.

As the silicon-containing material, for example, a simple substance of silicon, a silicon oxide (SiO x ), a silicon alloy, and a silicon compound can be used.
Examples of the silicon alloy include a Si—Ti alloy and a Si—Cu alloy.
An example of the silicon compound is silicon nitride (SiN x ).

  The porosity of the active material layer 20 is preferably 10 to 70%, and more preferably 30 to 60%. If the porosity of the active material layer 20 is 10% or more, the expansion relaxation effect of the active material layer 20 can be obtained. When the porosity exceeds 70%, the electrode plate can be used without any problem depending on the use of the battery, but the energy density of the electrode plate is small.

  The porosity of the active material layer 20 can be calculated from the weight and thickness of the active material layer having a certain area and the density of the active material. When the thickness of the active material layer of a certain area S is T, the weight of the active material layer is W, and the density of the active material is D, the porosity (%) is expressed by the formula: 100 [{ST− (W / D )} / ST].

  The porosity of the active material layer 20 can be controlled, for example, by adjusting the height of the protrusions, the size of the protrusions, the interval between the protrusions, and the like. When the growth direction of the columnar particles made of the active material is inclined with respect to the normal direction of the surface of the current collector, the growth direction of the columnar particles and the normal direction of the surface of the current collector The porosity of the negative electrode active material layer can be controlled by adjusting the angle formed by.

  The height H of the protrusion is preferably 1 to 15 μm, and more preferably 3 to 10 μm. When the height H of the protrusion is smaller than 1 μm, the stress absorption capacity of the protrusion is not sufficiently obtained, and the voids may not be sufficiently formed in the active material layer. As a result, the active material may be peeled off from the current collector or the electrode plate may be deformed, resulting in deterioration of the cycle characteristics of the battery. If the height H of the protrusions is greater than 15 μm, the total thickness of the electrode plate is increased, which may reduce the capacity density of the battery.

  Here, the height H of the protruding portion refers to the distance between the interface between the base material 11 and the protruding portion 12 and the highest position of the protruding portion 12. The height H of the protrusions is an average value obtained by cutting the current collector, measuring the heights of 2 to 10 protrusions by cross-sectional observation with an electron microscope, and averaging the obtained values.

  The size R of the protrusion is preferably 1 to 20 μm, and more preferably 3 to 15 μm. When the size R of the protrusion is larger than 20 μm, the size of the columnar active material particles formed on the protrusion is inevitably larger than 20 μm. Since the active material particles having such a large size have an extremely large expansion stress, the active material particles may be self-destructed. As a result, the active material may peel off from the current collector, and the cycle characteristics of the battery may deteriorate. When the size R of the protrusions is smaller than 1 μm, the stress absorbing power of the protrusions cannot be sufficiently obtained as described above, and the voids may not be sufficiently formed in the active material layer.

  Here, the size R of the protrusion refers to the maximum diameter of the protrusion as viewed from the normal direction of the surface of the current collector. The size R of the protrusion is obtained by measuring the maximum diameter of 2 to 10 protrusions from the normal direction of the surface of the current collector and averaging the obtained values using an electron microscope. Can be sought.

  The distance L between two adjacent protrusions is preferably 1 to 30 μm, and more preferably 15 to 30 μm. When the interval L between adjacent protrusions is smaller than 1 μm, adjacent columnar particles are integrated, and the porosity of the active material layer may be reduced. When the porosity of the active material layer decreases, the effect of relaxing the expansion stress of the active material may not be sufficiently obtained. If the interval L between adjacent protrusions is greater than 30 μm, columnar particles are formed in regions other than the protrusions, and the base material may be greatly deformed by the expansion stress of the active material.

  Here, the interval L between adjacent protrusions refers to the distance between the central axes of the protrusions. The central axis refers to an axis that passes through the center of the shape of the protrusion when viewed from the normal direction of the current collector surface and is parallel to the normal direction of the current collector surface. The interval between adjacent protrusions is an average value obtained by cutting the current collector, measuring the interval between 2 to 10 adjacent protrusions by cross-sectional observation with an electron microscope, and averaging the obtained values.

  In addition, it is preferable that the space | interval between two protrusion parts adjacent on the shortest distance is 1-30 micrometers, and it is more preferable that it is 15-30 micrometers. For example, when the interval between two adjacent protrusions is the shortest in the direction parallel to the arrow 21 in FIG. 2, the interval between the two adjacent protrusions is preferably within the above range. At this time, for example, also in the direction parallel to the arrow 22 and / or the direction parallel to the arrow 23, the interval between two adjacent protrusions may be within the above range.

  The shape of the protrusion when viewed from the normal direction of the current collector may be a circle as shown in FIG. 2, an ellipse, a rhombus, or the like. In the oval and rhombus, the intersection between the major axis and the minor axis is the center, and the axis passing through the center and perpendicular to the normal direction of the surface of the current collector is the center axis.

  The height and size of the protrusions after annealing, and the distance between two adjacent protrusions are preferably in the above ranges, as in the case of the protrusions before annealing.

  The protrusion 12 preferably contains copper having a purity of 99.9% by weight or more. As the copper having a purity of 99.9% by weight or more, for example, tough pitch copper may be used. Tough pitch copper refers to a copper material containing 99.9% by weight or more of copper and 0.02 to 0.05% by weight of oxygen.

  By using such a protrusion made of copper having a purity of 99.9% by weight or more, the expansion stress of the active material layer can be sufficiently absorbed.

The Vickers hardness of the substrate 11 is desirably 140 or more, and more desirably 200 or more.
As such a base material 11, nickel foil, stainless steel foil, or copper alloy foil can be used, for example. The copper alloy foil preferably contains at least one element selected from the group consisting of Ni, Si, Sn, Be, Co, Ti, Fe, and Zr. For example, when the copper alloy foil contains at least one element selected from the group consisting of Ni, Si, Sn, Be, Co, Ti, and Fe, the copper alloy foil contains 0.1 to 10 elements. The content is preferably 1% by weight, more preferably 0.2 to 3% by weight.

  Depending on the type of metal element added to the copper alloy, even if the amount of the metal element is very small, that is, the copper concentration is 99.9% by weight or more, the Vickers hardness is 140 or more. be able to. For example, by adding 0.015 to 0.03% by weight of Zr, a copper alloy having a high annealing temperature, that is, a high hardness can be formed. Here, the copper alloy containing the metal element cannot be formed unless the metal element is intentionally added to copper. That is, in the method for forming the protrusion as described below, it is considered that the metal element is not included in the protrusion unless the metal element is intentionally added.

  By using a base material made of such a material, it is possible to sufficiently suppress deformation of the electrode plate due to stress when the active material layer expands.

  The Vickers hardness of the protrusion 12 and the substrate 11 is in the above range, and the difference between the Vickers hardness of the protrusion and the Vickers hardness of the substrate is preferably 50 or more, and more preferably 70 or more. preferable. Thereby, the expansion stress of the active material layer can be absorbed by the protrusion, and even if the stress propagates to the base material, the base material can be prevented from being deformed. When the protrusion is annealed, if the difference between the Vickers hardness of the protrusion after annealing and the Vickers hardness of the substrate is 50 or more, the Vickers hardness immediately after the formation of the protrusion and the Vickers hardness of the substrate The difference may be less than 50.

The protrusion 12 is preferably formed by a plating method, a vapor deposition method, a sputtering method, or a sintering method in which the constituent material of the protrusion and the base material are sintered. If the protruding portion is manufactured by the manufacturing method, it is not necessary to machine the protruding portion. Therefore, it is possible to maintain a state in which the protruding portion including the surface layer portion is easily plastically deformed.
Further, by using the manufacturing method, for example, a protrusion made of copper having a purity of 99.9% by weight or more can be formed.

  On the other hand, in the conventionally used machining method, for example, the top surface of the protrusion is compressed. Specifically, for example, in the method of forming irregularities on the surface of the current collector by sandwiching the current collector with these two rollers using two rollers provided with concave portions of a predetermined pattern on the surface, The top surface of the protrusion is compressed by the roller. For this reason, a projection part becomes difficult to deform | transform.

Hereinafter, a method for forming the protrusion will be described in detail.
(I) The protrusions can be formed by plating or vapor deposition (or sputtering) as follows, for example.
First, a resist layer having openings having a predetermined pattern is formed on a substrate by a photoresist method.
Specifically, a resist is applied on the substrate to form a resist layer. Next, the resist layer is exposed using a glass mask or a resin mask on which a predetermined pattern (for example, 1 to 20 μm circular or polygonal dots) is printed. Next, the resist layer having an opening having a predetermined pattern can be obtained by developing with an alkaline aqueous solution, washing with water, and drying.

  As the resist, both a liquid resist and a dry film resist can be used. The resist may be a negative type or a positive type. The thickness of the resist layer is desirably three times or more the height of the protrusion.

Next, a protrusion is formed by a plating method.
The substrate containing the resist layer after development is immersed in an electrolytic solution containing the constituent material (metal ions) of the protrusion, and the protrusion is formed by plating the metal in the opening of the resist layer. . By the plating method, for example, a protrusion made of copper having a purity of 99.9% by weight or more can be formed.

Alternatively, the protrusion can be formed on the substrate by using a vapor deposition method or a sputtering method using the constituent material of the protrusion as a target.
Specifically, a substrate having a resist layer having openings with a predetermined pattern is obtained as described above. Next, the constituent material of the protrusion is deposited on the base material by vapor deposition or sputtering using the constituent material of the protrusion as a target.
As the target, for example, it is preferable to use copper having a purity of 99.9% by weight.

(Ii) Formation of the protrusions by the sintering method can be performed, for example, as follows.
First, a slurry containing predetermined conductive material particles is prepared. The obtained slurry is applied to a substrate. Next, the slurry and the substrate are sintered at a predetermined temperature. Thus, the protrusion can be formed on the substrate.

  The median particle size of the conductive material particles is preferably 1 to 10 μm. If the median particle diameter of the particles is smaller than 1 μm, effective protrusions may not be obtained. If the median particle size of the particles is larger than 10 μm, the protrusions may not be formed at appropriate intervals. For this reason, when an active material layer is formed, a sufficient space may not be formed in the active material layer.

  The sintering temperature is desirably 500 ° C to 700 ° C. For example, when copper particles are used as the conductive material particles, the copper particles can be sintered in this temperature range.

  The protrusions may be regularly arranged as shown in FIG. 2 or irregularly arranged as shown in FIG. 3 as long as the interval L between adjacent protrusions is within the above range. May be. FIG. 3 shows the current collector 30 in which the protrusions 32 are irregularly arranged on the base material 31.

For example, a current collector as shown in FIG. 1 in which protrusions made of copper are regularly arranged can be produced by, for example, the plating method or the vapor deposition method (or sputtering method).
First, as described above, a resist layer having openings of a predetermined pattern is formed on a substrate by a photoresist method. For example, at this time, a glass mask or a resin mask on which circular or polygonal dots of 1 to 20 μm are printed can be used.

  Next, a protrusion is formed by a plating method. If the base material including the resist layer after development is immersed in a copper sulfate bath and copper is plated on the opening of the resist, the protrusions made of copper can be regularly arranged.

  Or the protrusion part which consists of copper can also be formed in the base material containing the resist layer after image development using a vapor deposition method or a sputtering method.

The current collector as shown in FIG. 3 in which the protrusions made of copper are irregularly arranged can be formed by, for example, a plating method in which the protrusions made of copper are grown in the form of particles. In such a plating method, metal particles having a predetermined size can be grown on the surface of the substrate by using a current density higher than that of a normal plating method (for example, a limit current density or more).
Or the protrusion part which consists of copper can also be irregularly arranged on a base material by the said sintering method.

  In the present invention, the conductive material constituting the protrusion may be other than copper as long as it easily undergoes plastic deformation. Protrusions made of a metal other than copper can also be basically produced by the method described above.

  The columnar particles supported on the surface of the current collector may be composed of a single part as shown in FIG. 1, or a laminate of a plurality of grain layers as shown in FIGS. May be configured. Further, the growth direction of the columnar particles may be inclined with respect to the normal direction of the surface of the current collector as shown in FIG. The average growth direction of the entire columnar particles may be parallel to the normal direction of the surface of the current collector as shown in FIGS.

  5 and 6 schematically show active material particles contained in an electrode plate according to another embodiment of the present invention. 5 and 6, the same components as those in FIG. 1 are denoted by the same reference numerals.

The active material layer 20 in FIG. 1 can be produced using, for example, a vapor deposition apparatus 40 having an electron beam heating means (not shown) as shown in FIG.
The vapor deposition apparatus 40 includes a gas pipe 44 and a nozzle 43 for introducing oxygen gas into the chamber 41. The nozzle 43 is connected to a gas pipe 44 introduced into the vacuum chamber 41. The gas pipe 44 is connected to an oxygen cylinder (not shown) via a mass flow controller (not shown).

A fixed base 42 for fixing the current collector 10 is installed above the nozzle 43. A target 45 is installed vertically below the fixed base 42. An oxygen atmosphere composed of oxygen gas exists between the current collector 10 and the target 45.
For the target 45, a material containing silicon, for example, a simple substance of silicon can be used.

  The current collector 10 in which the protrusions as shown in FIG. 2 are regularly arranged is fixed to the fixing base 42, and the fixing base 42 is inclined so as to form an angle α with the horizontal plane.

  When silicon alone is used as the target 45, silicon atoms are evaporated from the target 45 when the target 45 is irradiated with an electron beam. The evaporated silicon atoms pass through the oxygen atmosphere and are deposited on the current collector together with the oxygen atoms. In this way, an active material layer containing silicon oxide is formed on the current collector. At this time, silicon atoms are deposited together with oxygen atoms in a concentrated manner on the protrusions 12 of the current collector. For this reason, as shown in FIG. 1, the active material layer is composed of a plurality of columnar particles 21 containing silicon oxide formed on the protrusions.

  The columnar particle 50 in FIG. 5 has a laminate including eight grain layers 50a, 50b, 50c, 50d, 50e, 50f, 50g, and 50h. In the columnar particle 50 of FIG. 5, the growth direction of the particle layer 50a is inclined in a predetermined first direction with respect to the normal direction of the surface of the current collector. The growth direction of the grain layer 50b is inclined in a second direction different from the first direction with respect to the normal direction of the surface of the current collector. Similarly, the particle layer included in the columnar particles 50 is alternately inclined in the first direction and the second direction with respect to the normal direction of the surface of the current collector. Thus, by alternately changing the growth direction of the grain layer between the first direction and the second direction when laminating a plurality of grain layers, the average growth direction as the whole grain of the columnar grain 50 is It can be made parallel to the normal direction of the surface of the current collector.

  Alternatively, if the growth direction of the entire columnar particle is parallel to the normal direction of the surface of the current collector, the growth direction of each grain layer may be inclined in different directions.

  The columnar particles in FIG. 5 can be produced, for example, as follows. First, the grain layer 50a is formed so as to cover the top of the protrusion 12 and a part of the side surface following the top. Next, the grain layer 50b is formed so as to cover the remaining side surface of the protrusion 12 and a part of the top surface of the grain layer 50a. That is, in FIG. 5, the grain layer 50 a is formed at one end including the top of the protrusion 12, and the grain layer 50 b partially overlaps the grain layer 50 a, but the remaining part is the other part of the protrusion 12. Formed at the end. Further, the grain layer 50c is formed so as to cover the rest of the top surface of the grain layer 50a and a part of the top surface of the grain layer 50b. That is, the grain layer 50c is formed so as to mainly contact the grain layer 50a. Further, the particle layer 50d is formed mainly in contact with the particle layer 50b. Similarly, columnar particles as shown in FIG. 5 are formed by alternately laminating the particle layers 50e, 50f, 50g, and 50h.

The columnar particle 60 of FIG. 6 has a plurality of first particle layers 61 and a plurality of second particle layers 62.
The thickness of each particle layer of the columnar particles in FIG. 6 is thinner than the thickness of the particle layer of the columnar particles in FIG. Moreover, the outline of the columnar particle of FIG. 6 is smooth compared with the columnar particle of FIG.

  Also in the columnar particles of FIG. 6, if the average growth direction of the columnar particles as a whole is parallel to the normal direction of the current collector surface, the growth direction of each particle layer is the normal of the current collector surface. It may be inclined from the direction. In the columnar particle of FIG. 6, the growth direction of the first grain layer 61 is the A direction, and the growth direction of the second grain layer 62 is the B direction.

  An active material layer including columnar particles as shown in FIG. 5 can be produced using, for example, a vapor deposition apparatus 70 as shown in FIG. FIG. 7 is a side view schematically showing the configuration of the vapor deposition apparatus 70. In FIG. 7, the same components as those in FIG. 4 are given the same numbers, and descriptions thereof are omitted.

  A fixing base 71 which is a plate-like member is supported in the chamber 41 so as to be angularly displaced or rotatable, and the current collector 10 is fixed to one surface in the thickness direction thereof. The angular displacement of the fixed base 71 is performed between a position indicated by a solid line and a position indicated by a one-dot broken line in FIG. In the position indicated by the solid line, the surface of the fixed base 71 on the side where the current collector 10 is fixed faces the target 45 in the vertical direction, and the angle formed by the fixed base 71 and the horizontal straight line is γ °. Position (position A). The position indicated by the one-dot broken line is such that the surface of the fixed base 71 on the side where the current collector 10 is fixed faces the lower target 45 in the vertical direction, and the angle formed by the fixed base 71 and the horizontal straight line is (180− It is a position (position B) that is γ) °. The angle γ ° can be appropriately selected according to the dimensions of the active material layer to be formed.

  In the manufacturing method of the active material layer using the vapor deposition apparatus 70, first, the current collector 10 is fixed to the fixing base 71, and oxygen gas is introduced into the chamber 41. In this state, the target 45 is irradiated with an electron beam and heated to generate the vapor. For example, when silicon is used as a target, vaporized silicon passes through an oxygen atmosphere, and silicon oxide is deposited on the surface of the current collector. At this time, by arranging the fixing base 71 at the position of the solid line, the grain layer 50a shown in FIG. Next, the fixed bed 71 is angularly displaced to the position of the one-dot broken line to form the grain layer 50b shown in FIG. Thus, by moving the fixed base 71 alternately between the position A and the position B, the columnar particles 50 having eight grain layers shown in FIG. 5 are formed.

  The columnar particles 60 shown in FIG. 6 can also be produced basically in the same manner as the columnar particles of FIG. 5 using the vapor deposition apparatus of FIG. The columnar particles 60 in FIG. 6 can be produced, for example, by shortening the vapor deposition time at the positions A and B as compared with the columnar particles in FIG. 5 and increasing the number of stacked particle layers.

  In any of the above production methods, if the protrusions are regularly arranged on the current collector surface and an active material layer composed of a plurality of columnar particles containing silicon is formed on the current collector, the columnar particles Gaps can be formed at regular intervals between them.

  Note that in the case where the active material layer is provided only on one side of the current collector, the protrusions may be provided only on the side of the base material on which the active material layer is provided. Furthermore, you may provide an active material layer on both surfaces of the electrical power collector in which the projection part was formed in both surfaces.

  In addition to the above, the active material layer containing silicon oxide is used by targeting silicon oxide without using an oxygen atmosphere between the current collector and the target, and using the silicon oxide as a current collector. It can also be produced by depositing. Alternatively, silicon nitride can be deposited on the current collector by using a nitrogen atmosphere instead of an oxygen atmosphere and using a simple substance of silicon as a target.

  Furthermore, the active material particles, for example, active material particles made of silicon alone or active material particles made of a silicon alloy in the vapor deposition apparatus are materials (including mixtures) containing elements constituting silicon alone or silicon alloys. As a target and can be produced by evaporation under vacuum.

  The negative electrode current collector contained in the battery can be observed by removing the negative electrode active material layer from the negative electrode current collector. For example, a charged lithium ion secondary battery is disassembled and the negative electrode is taken out. When the negative electrode is immersed in water, lithium existing in the negative electrode reacts rapidly with water, and the negative electrode active material is easily separated from the current collector. That is, the active material can be easily removed from the current collector by immersing the charged negative electrode in water.

  The electrode plate 1 as described above is preferably used as a negative electrode for a lithium secondary battery including a negative electrode active material containing silicon. FIG. 8 shows a lithium secondary battery according to an embodiment of the present invention.

The battery 80 in FIG. 8 includes a stacked electrode plate group and an electrolyte (not shown) housed in a battery case 84. The electrode plate group includes a positive electrode 81, a negative electrode 82, and a separator 83 disposed between the positive electrode 81 and the negative electrode 82. As described above, the negative electrode 82 includes the current collector 82a including the base material and the protrusions supported thereon, and the negative electrode active material layer 82b. The negative electrode active material layer 82b includes, for example, a plurality of columnar negative electrode active material particles carried on the protrusions. In the battery of FIG. 8, the negative electrode active material layer is provided only on one side of the negative electrode current collector.
The positive electrode 81 includes a positive electrode current collector 81a and a positive electrode active material layer 81b supported on one surface thereof.

  One end of the negative electrode lead 86 is connected to the surface of the negative electrode current collector 82a where the negative electrode active material layer is not formed, and the surface of the positive electrode current collector 81a where the positive electrode active material layer is not formed is connected to the positive electrode One end of the lead 85 is connected.

  The battery case 84 has openings at positions opposite to each other, and the other end of the positive electrode lead 85 extends from one opening of the battery case 84 to the outside. The other end of the negative electrode lead 86 is extended to the outside from the opening. The opening of the battery case 84 is sealed with a sealing material 87.

  Examples of the material constituting the positive electrode current collector include materials known in the art. An example of such a material is aluminum.

  The positive electrode active material layer can include, for example, a positive electrode active material, a binder, and a conductive agent. As the positive electrode active material and the binder added to the positive electrode, materials known in the art can be used. As the positive electrode active material, for example, a lithium-containing composite oxide such as lithium cobalt oxide can be used.

  Examples of the binder added to the positive electrode include polytetrafluoroethylene and polyvinylidene fluoride.

  Examples of the conductive agent added to the positive electrode include natural graphite (such as flake graphite), graphite such as artificial graphite and expanded graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, and the like. Carbon blacks, conductive fibers such as carbon fibers and metal fibers, metal powders such as copper and nickel, and organic conductive materials such as polyphenylene derivatives can be used. These may be used alone or in combination of two or more.

  The electrolyte includes a non-aqueous solvent and a solute dissolved therein. Examples of the non-aqueous solvent include, but are not limited to, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and the like. These nonaqueous solvents may be used alone or in combination of two or more.

Examples of the solute include LiPF 6 , LiBF 4 , LiCl 4 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCl, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (CF 2 SO 2 ) 2 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , LiB 10 Cl 10 , and imides can be used. These may be used alone or in combination of two or more.

  As a material constituting the separator, a material known in this field can be used. Examples of such a material include polyethylene, polypropylene, a mixture of polyethylene and polypropylene, or a copolymer of ethylene and propylene.

  The shape of the lithium ion secondary battery including the negative electrode is not particularly limited, and may be, for example, a coin type, a sheet type, or a square type. The lithium ion secondary battery may be a large battery used for an electric vehicle or the like. The electrode plate group included in the lithium ion secondary battery of the present invention may be a laminated type as described above or a wound type.

Example 1
A stacked lithium secondary battery as shown in FIG. 8 was produced.
(I) Production of positive electrode 10 g of lithium cobaltate (LiCoO 2 ) powder having an average particle diameter of about 10 μm as a positive electrode active material, 0.3 g of acetylene black as a conductive agent, and polyvinylidene fluoride powder as a binder. 8 g and an appropriate amount of N-methyl-2-pyrrolidone (NMP) were sufficiently mixed to prepare a positive electrode mixture paste. The obtained paste was applied to one side of a positive electrode current collector made of an aluminum foil having a thickness of 20 μm, dried, and rolled to form a positive electrode active material layer.

  Thereafter, the obtained positive electrode plate was cut into a predetermined shape to obtain a positive electrode. In the obtained positive electrode, the thickness of the positive electrode active material layer carried on one surface of the positive electrode current collector was 70 μm, and the size of the active material layer was 30 mm × 30 mm. An aluminum positive electrode lead was connected to the surface of the current collector not having the positive electrode active material layer.

(Ii) Production of negative electrode Copper alloy foil (manufactured by Hitachi Cable Ltd.) (copper is 96.45 wt%, nickel is 2.5 wt%, and silicon is 0.5 wt%) (thickness: 18 μm) was used as the substrate. Protrusions made of copper were formed on the substrate by plating.

A dry film resist (manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 25 μm was attached to one surface of the copper alloy foil.
A circular dot having a diameter of 10 μm was printed on a resin mask with a center interval of 20 μm. The resin mask was placed on the dry film resist. Using a parallel exposure machine, the resist was exposed by irradiating i-line (ultraviolet light centered at a wavelength of 365 nm) from above the resin mask. Then, it developed with aqueous alkali solution and formed the resist layer which has the opening part of a predetermined pattern.

Next, a copper alloy foil provided with a resist layer having an opening was immersed in an electrolytic solution containing copper sulfate pentahydrate 270 g / L and sulfuric acid 100 g / L as a cathode. A copper layer having a thickness of 8 μm was formed on the copper alloy foil under the conditions of a current density of 5 A / dm 2 and a liquid temperature of 50 ° C.

  Thereafter, the resist layer was removed, and protrusions made of regularly arranged copper were formed on the copper alloy foil. From the difference in the analysis results of the copper alloy foil using the inductively coupled plasma (ICP) emission analysis method and the copper alloy foil in which the protrusions were formed, the purity of the copper in the formed protrusions was 99.9% by weight. Further, the impurities contained in the protrusions were mainly organic substances of oxygen and resist residues.

  The height of the protrusions was 8 μm, the size of the protrusions was 10 μm, and the interval between adjacent protrusions was 20 μm. The protrusion was formed only on one surface of the copper alloy foil.

  As a result of measuring the hardness of the surface of the copper alloy foil with a Vickers hardness meter, the Vickers hardness of the copper alloy foil as the base material was 250. Further, the Vickers hardness of the protrusion was measured as follows. A copper layer was plated on the entire surface of the copper alloy foil without forming a resist layer. The Vickers hardness of the formed copper layer was measured. As a result, the Vickers hardness of the copper layer was 120. The Vickers hardness of this copper layer was defined as the Vickers hardness of the protrusion made of copper.

Next, a negative electrode active material layer was produced using a vapor deposition apparatus (manufactured by ULVAC, Inc.) having an electron beam heating means (not shown) as shown in FIG.
From the nozzle provided in the vapor deposition apparatus, oxygen gas having a purity of 99.7% (manufactured by Nippon Oxygen Co., Ltd.) was released at a flow rate of 80 sccm. As a target, silicon simple substance (manufactured by Kojundo Chemical Laboratory Co., Ltd.) having a purity of 99.9999% was used.

  The current collector obtained as described above was cut into a size of 40 mm × 40 mm, and the current collector after cutting was fixed to a fixed base. The angle α formed by the fixing base and the horizontal plane was 60 °. The thickness of the current collector was 35 μm.

  The acceleration voltage of the electron beam applied to the target was set to -8 kV, and the emission was set to 500 mA. After passing through the oxygen atmosphere, the vapor of silicon alone was deposited on the current collector fixed to the fixed base. The deposition time was set to 22 minutes. In this way, a negative electrode plate was obtained that includes columnar silicon oxide particles and an active material layer on the current collector in which the growth direction of the columnar particles is inclined with respect to the normal direction of the surface of the current collector. In the obtained negative electrode plate, an active material layer was formed only on one side of the current collector. The thickness T of the active material layer was 17 μm.

The amount of oxygen contained in the negative electrode active material was quantified by a combustion method. As a result, the composition of the negative electrode active material containing silicon and oxygen was SiO 0.5 .

The porosity of the negative electrode active material layer was determined as follows. In the obtained negative electrode plate, the area S of the region where the negative electrode active material layer was formed was 961 mm 2 (31 mm × 31 mm).
The weight W of the active material layer was determined by subtracting the weight of the negative electrode current collector from the weight of the obtained negative electrode plate. The volume (W / D) of the active material layer was determined from the weight W of the active material layer and the density D of SiO 0.5 (2.3 g / cm 3 ). The total space volume (S × T) of the active material layer was determined from the thickness T (17 μm) of the active material layer and the area S (961 mm 2 ) of the region of the current collector carrying the active material layer. Using the volume (W / D) of the obtained active material layer and the total space volume (S × T) of the active material layer, the porosity P (= 100 [{ST− (W / D)}} of the active material layer / ST]). As a result, the porosity of the active material layer was 40%.
In the above calculations, the true density of Si and (2.33g / cm 3) the average of the true densities of SiO (2.24g / cm 3), and the density of SiO 0.5.

Next, metallic lithium was vapor-deposited on the surface of the obtained negative electrode plate as follows using a resistance heating vapor deposition apparatus (manufactured by ULVAC, Inc.).
A negative electrode plate and a tantalum boat were placed in the vapor deposition apparatus, and a predetermined amount of metallic lithium was loaded into the boat. The boat was fixed so as to face the active material layer of the negative electrode plate.

The value of the current flowing through the boat was set to 50 A, and vapor deposition was performed for 10 minutes. In this way, the negative electrode active material made of SiO 0.5 was supplemented with irreversible capacity lithium stored at the first charge / discharge. Thereafter, the negative electrode plate on which metallic lithium was deposited was cut into a size of 31 mm × 31 mm to obtain a negative electrode 1A.
A negative electrode lead made of nickel was connected to the surface of the negative electrode current collector not having the negative electrode active material layer.

(Iii) Battery assembly A separator (made by Asahi Kasei Co., Ltd.) made of a polyethylene microporous film having a thickness of 20 μm is disposed between the positive electrode and the negative electrode obtained as described above, and a laminated electrode plate group Was made. At this time, the positive electrode and the negative electrode were arranged so that the positive electrode active material layer and the negative electrode active material layer were opposed to each other with a separator interposed therebetween.

The obtained electrode plate group was inserted into a battery case made of an aluminum laminate sheet together with an electrolyte.
The electrolyte was prepared by mixing ethylene carbonate and ethyl methyl carbonate at a volume ratio of 1: 1 and dissolving LiPF 6 in this mixed solvent at a concentration of 1.0 mol / L.

  The positive electrode active material layer, the negative electrode active material layer, and the separator were impregnated with the electrolyte by leaving for a predetermined time. Thereafter, the positive electrode lead and the negative electrode lead are respectively extended from the openings located in opposite directions of the battery case to the outside. And sealed. Thus, the battery was completed. The obtained battery is referred to as battery 1A.

<< Comparative Example 1 >>
Protrusions were formed on the surface of the substrate by machining. That is, the protrusion part formed in the surface had the same composition as the copper alloy foil which is a base material, and had the same Vickers hardness as a base material.
A current collector was produced using the apparatus shown in FIG. 9 including a processing roll 91 for forming irregularities and a backup roll 92 that supports the processing roll 91. In addition, as the process roll 91 for uneven | corrugated formation, the iron roll provided with the chromium oxide layer which has the hole formed regularly was used. The chromium oxide layer was formed by spraying chromium oxide on an iron roll. The holes were formed by laser processing. The hole diameter was 10 μm and the hole depth was 11 μm. The distance between the centers of adjacent holes was 20 μm.

  The base material (copper alloy foil) 93 used in Example 1 was disposed between the work rolls 91, and protrusions were formed on both surfaces of the copper alloy foil at a linear pressure of 3 t / cm. The size of the formed protrusion was 9 μm. The obtained current collector was sectioned, and the section was observed with an electron microscope. As a result, the height of the protrusion was 3 μm. The Vickers hardness of the substrate and the protrusion was 250.

  A comparative negative electrode 1B was produced in the same manner as in Example 1 except that the obtained current collector was used. A comparative battery 1B was produced in the same manner as in Example 1 except that the comparative negative electrode 1B was used.

<< Comparative Example 2 >>
A copper alloy foil (manufactured by Hitachi Cable Ltd.) containing 0.03% by weight of zirconia (Zr) was used as a base material, and protrusions were formed on the surface of the base material by machining.
A copper alloy foil containing 0.03% by weight of zirconia is placed between processing rolls in the same manner as in Comparative Example 1, and is pressure-formed at a linear pressure of 3 t / cm to obtain a current collector having protrusions on both sides. It was. A comparative negative electrode 1C was produced in the same manner as in Example 1 except that the obtained current collector was used. The size of the formed protrusion was 9 μm. The height of the protrusion was 4 μm. The Vickers hardness of the base material and the protrusion was 150.
A comparative battery 1C was produced in the same manner as in Example 1 except that the comparative negative electrode 1C was used.

<< Comparative Example 3 >>
Using a tough pitch copper foil (manufactured by Hitachi Cable Ltd.) as a base material, protrusions were formed on the surface of the base material by machining.
Similar to Comparative Example 1, the tuft tip copper foil was placed between the processing rolls and was pressure-molded at a linear pressure of 2 t / cm to obtain a current collector having protrusions on both sides. A comparative negative electrode 1D was produced in the same manner as in Example 1 except that the obtained current collector was used. The size of the formed protrusion was 9 μm. The height of the protrusion was 6 μm. The Vickers hardness of the base material and the protrusion was 120.
A comparative battery 1D was produced in the same manner as in Example 1 except that the comparative negative electrode 1D was used.

  In Example 1, the negative electrode current collector is heated to 300 ° C. during the formation of the negative electrode active material. At such a temperature, only the protrusion made of copper having a purity of 99.9% by weight is annealed, and the Vickers hardness of the protrusion is lowered. Then, the Vickers hardness of the protrusion part after annealing was measured. However, since the Vickers hardness of the base material and the protruding portion cannot be measured after the active material is formed, the Vickers hardness of the protruding portion after heating only the negative electrode current collector at 300 ° C. for 22 minutes was measured.

Similarly, for the negative electrode current collectors used in Comparative Examples 1 to 3, the Vickers hardness of the protrusions was measured after heating at 300 ° C. for 22 minutes. In the case of tough pitch copper having a high copper concentration, both the protrusion and the base material are annealed by the heat treatment. That is, in the comparative electrode 1D using tough pitch copper, the protrusions after annealing and the Vickers hardness of the base material are the same.
Table 1 summarizes the configurations of the negative electrode current collectors of the negative electrode 1A and the comparative negative electrodes 1B to 1D.

[Evaluation methods]
(I) Cycle characteristics The batteries 1A and the comparative batteries 1B to 1D were each housed in a constant temperature bath of 20 ° C, and the batteries were charged by the following constant current and constant voltage method. First, each battery was charged at a constant current of a 1C rate (1C is a current value that can use up the entire battery capacity in one hour) until the battery voltage reaches 4.2V. After the battery voltage reached 4.2V, each battery was charged at a constant voltage of 4.2V until the current value reached 0.05C.
After resting for 20 minutes, the charged battery was discharged at a constant rate of 1C rate until the battery voltage reached 2.5V.
Such charge and discharge was repeated 100 cycles.

  The ratio of the total discharge capacity at the 100th cycle to the total discharge capacity at the 1st cycle was defined as the capacity maintenance rate. The results are shown in Table 2. In Table 2, the capacity maintenance rate is expressed as a percentage value.

  In any battery, lithium was deposited on the negative electrode to compensate for the irreversible capacity. For this reason, the capacity of each battery is regulated by the capacity of the positive electrode. That is, when the battery voltage is the discharge end voltage of 2.5 V, the positive electrode potential is 3 V and the negative electrode potential is 0.5 V on the basis of lithium. Discharging is terminated by a potential drop at the positive electrode.

  In the battery 1A, wrinkles were not generated on the electrode plate even after 100 cycles, and the capacity retention rate was also high. In the negative electrode current collector used for the battery 1A, the protrusions formed on the surface of the current collector are made of a material that easily undergoes plastic deformation and are not machined. For this reason, in the battery 1A, the protrusion can follow the expansion of the active material. Therefore, it is considered that the active material did not peel from the current collector. Furthermore, since the base material is less likely to be plastically deformed than the protrusions, the base material has a hardness that does not follow the expansion of the active material. For this reason, generation | occurrence | production of the wrinkle of the electrode plate was suppressed. Therefore, it is considered that good cycle characteristics were obtained in the battery 1A.

  On the other hand, in the comparative batteries 1B to 1C, the cycle characteristics were low as compared with the battery 1A. Further, the active material was peeled off at the interface between the active material and the protrusion. This is presumably because the protrusion has a hardness that cannot follow the expansion of the active material.

  In the comparative battery 1D, the protrusions are made of a material that can follow the expansion of the active material. However, since the base material is also made of the same material as the protrusions, it is considered that the expansion and contraction stress propagates to the base material and wrinkles occur in the electrode plate. As a result, the reactivity of the electrode plate becomes non-uniform and the charge / discharge becomes non-uniform, which is considered to have reduced the cycle characteristics.

Example 2
Except having changed the formation method of a projection part, it carried out similarly to Example 1, and produced the following negative electrodes 2A-2F. Further, batteries 2A to 2F were produced in the same manner as in Example 1 except that the negative electrodes 2A to 2F were used.

<I> Negative electrode 2A
The protrusion was formed by a vapor deposition method.
A resist layer having openings of a predetermined pattern was formed on the surface of the copper alloy foil used in Example 1 in the same manner as in Example 1. After this, copper was evaporated. The vapor deposition of copper was performed using a vapor deposition apparatus 40 (manufactured by ULVAC, Inc.) having an electron beam (EB) heating means as shown in FIG.

  A copper alloy foil provided with a resist layer having an opening was fixed to the fixing base 42. A copper simple substance (manufactured by Kojundo Chemical Laboratory Co., Ltd.) having a purity of 99.9% by weight was installed as a target vertically below the fixed base. The fixed base was fixed to be horizontal. The acceleration voltage of the electron beam applied to the copper target was set to -8 kV, and the emission was set to 100 mA.

The vapor of copper alone was deposited on the copper alloy foil installed on the fixed base 52 to form a copper layer. The deposition time was set to 20 minutes. The thickness of the copper layer was 8 μm. The resist layer on the substrate was removed with an alkaline aqueous solution to form regularly arranged protrusions on the substrate.
The height of the protrusion was 8 μm. The size of the protrusion was 10 μm. The interval between adjacent protrusions was 20 μm.

  A negative electrode 2A was produced in the same manner as in Example 1 except that this current collector was used.

By depositing copper on the entire surface of the copper alloy foil without forming a resist layer, and measuring the hardness of the deposited copper film with a Vickers hardness tester. Asked. As a result, the Vickers hardness of the protrusion was 160.
The purity of the formed protrusions was 99.9% by weight.

<Ii> Negative electrode 2B
On the surface of the copper alloy foil used in Example 1, irregularly arranged protrusions were formed by plating copper in a hump shape as follows.
By immersing a copper alloy foil as a cathode in an electrolytic solution containing 47 g / L of copper sulfate pentahydrate and 100 g / L of sulfuric acid, and plating at a current density of 30 A / dm 2 and a liquid temperature of 50 ° C. A hump-shaped protrusion was formed. Further, on this copper electrodeposit, copper plating was performed in an electrolytic solution containing 235 g / L of copper sulfate pentahydrate and 100 g / L of sulfuric acid under the conditions of a liquid temperature of 50 ° C. and a current density of 3 A / dm 2. The adhesion of the hump-like protrusions to the copper alloy foil was improved. The height of the protrusion formed by plating was irregular and was 1 to 41 μm. The size of the protrusion was 1 μm, and the shape of the protrusion was almost spherical. The interval between adjacent protrusions was 6 μm.
A negative electrode 2B was produced in the same manner as in Example 1 except that this current collector was used.

By subjecting the surface of the copper alloy foil to Vickers hardness of the hump-like protrusions under the same conditions as described above, uniformly plating the copper, and measuring the hardness of the formed copper plating layer with a Vickers hardness meter, Asked. As a result, the Vickers hardness of the protrusion was 120.
The purity of the formed protrusions was 99.9% by weight.

<Iii> Negative electrode 2C
Protrusions were formed by a sintering method.
A slurry in which copper particles having an average particle diameter of 8 μm were dispersed in N-methyl-2-pyrrolidone (NMP) was prepared. In the obtained slurry, the proportion of copper particles was 50% by weight. The purity of the copper particles was 99.9% by weight.
The obtained slurry was thinly applied to the surface of the copper alloy foil used in Example 1. Thereafter, the copper alloy foil coated with the slurry was heat-treated at 120 ° C. to volatilize NMP.

  Next, the copper alloy foil was heat-treated at 600 ° C. in a nitrogen stream to sinter the copper particles and the copper alloy foil. Thus, a current collector was obtained in which the copper particles were bonded as protrusions to the surface of the copper alloy foil. The height of the protrusion was 7 μm. The size of the protrusion was 8 μm. The interval between adjacent protrusions was 13 μm.

The Vickers hardness of the protrusion was determined by sintering the copper particles to a thickness of 5 mm and measuring the Vickers hardness of the obtained sintered film. As a result, the Vickers hardness of the protrusion was 130.
The purity of the formed protrusions was 99.9% by weight.

  A negative electrode 2C was produced in the same manner as in Example 1 except that this current collector was used.

<Iv> Negative electrode 2D
A negative electrode 2D was produced in the same manner as the negative electrode 2C, except that copper particles having an average particle diameter of 0.5 μm (purity: 99.9% by weight) were used. The height of the protrusion was 0.5 μm. The size of the protrusion was 0.5 μm. The interval between adjacent protrusions was 1 μm.

The Vickers hardness of the protrusion was determined by sintering the copper particles to a thickness of 5 mm and measuring the Vickers hardness of the obtained sintered film. As a result, the Vickers hardness of the protrusion was 130.
The purity of the formed protrusions was 99.9% by weight.

  A negative electrode 2D was produced in the same manner as in Example 1 except that this current collector was used.

<V> Negative electrode 2E
A negative electrode 2E was produced in the same manner as in Example 1 except that the height of the protrusion was 15 μm. The size of the protrusion and the interval between adjacent protrusions are the same as those of the negative electrode 1A.

<Vi> Negative electrode 2F
A negative electrode 2F was produced in the same manner as in Example 1 except that the height of the protrusion was 20 μm. The size of the protrusion and the interval between adjacent protrusions are the same as those of the negative electrode 1A.

In the negative electrodes 2A to 2F, the protrusion is made of copper having a purity of 99.9% by weight. Also in these negative electrodes, as in Example 1, when the negative electrode active material layer is formed, the protrusions are annealed, and the Vickers hardness of the protrusions decreases. Therefore, the Vickers hardness of the protrusion after annealing was measured in the same manner as in Example 1.
Table 3 summarizes the configurations of the negative electrodes 2A to 2F.

  The capacity maintenance rates of the batteries 2A to 2F were measured in the same manner as described above. The results are shown in Table 4.

From the results of the battery 2A, it was found that if the Vickers hardness of the protrusion after forming the active material layer (that is, after annealing) is 90 or less, the cycle characteristics are excellent.
From the results of the batteries 2B to 2D, it was found that the method of plating the copper and the method of sintering the copper particles are effective as the method for producing the protrusion.

  Moreover, it turned out that the height of a projection part is 1 micrometer or more. Thereby, it is possible to secure an appropriate porosity of the active material layer and sufficiently relax the stress during expansion of the active material.

  From the results of the batteries 2E to 2F, it was found that excellent cycle characteristics can be obtained even when the height of the protrusion is 20 μm. However, when the height of the protrusion is 15 μm or more, the porosity of the active material layer is the same, and the cycle characteristics are also the same.

  On the other hand, when the height of the protrusion is 20 μm, if the protrusion is formed on both sides of the current collector, the total thickness of the protrusion is only 40 μm. When the thickness of the protruding portion is increased, the proportion of the space that does not contribute to the battery volume increases, so that a high-capacity battery cannot be designed.

  From the above results, the height of the protrusions is preferably 1 μm or more and 15 μm or less.

Example 3
Except having changed the kind of base material, it carried out similarly to Example 1, and produced the following negative electrodes 3A-3D. Further, batteries 3A to 3D were produced in the same manner as in Example 1 except that the negative electrodes 3A to 3D were used.

<I> Negative electrode 3A
3 A of negative electrodes were produced like Example 1 except having used nickel foil as a base material. The nickel foil used had a Vickers hardness of 300.
The height of the protrusions was 8 μm, the size of the protrusions was 10 μm, and the interval between adjacent protrusions was 20 μm.

<Ii> Negative electrode 3B
A negative electrode 3B was produced in the same manner as in Example 1 except that stainless steel foil was used as the substrate. The stainless steel foil used had a Vickers hardness of 200.
The height of the protrusions was 8 μm, the size of the protrusions was 10 μm, and the interval between adjacent protrusions was 20 μm.

<Iii> Negative electrode 3C
A negative electrode 3C was produced in the same manner as in Example 1 except that a copper alloy foil containing 0.5% by weight of tin (Sn) was used as the base material. The copper alloy foil had a Vickers hardness of 140.
The height of the protrusions was 8 μm, the size of the protrusions was 10 μm, and the interval between adjacent protrusions was 20 μm.

<Iv> Negative electrode 3D
A negative electrode 3D was produced in the same manner as in Example 1 except that a copper alloy foil containing 0.03% by weight of zirconia (Zr) was used as the base material. The copper alloy foil had a Vickers hardness of 150.
The height of the protrusions was 8 μm, the size of the protrusions was 10 μm, and the interval between adjacent protrusions was 20 μm.

In the negative electrodes 3A to 3D, the protrusions are the same as those in the first embodiment. For these negative electrodes, the Vickers hardness of the protrusions after annealing was measured in the same manner as in Example 1.
Table 5 summarizes the configurations of the negative electrodes 3A to 3D.

  The capacity maintenance rates of the batteries 3A to 3D were measured in the same manner as described above. The results are shown in Table 6.

  When the substrate was a nickel foil, a stainless steel foil, a tin copper alloy foil, or a zirconia copper alloy foil, no wrinkles were formed on the electrode plate even after 100 cycles of charge and discharge. This is considered to be because the stress due to the expansion and contraction of the active material was absorbed by the protrusions and did not propagate to the base material. Further, from the results in Table 6, it was found that the cycle characteristics were excellent in any base material.

Example 4
Negative electrodes 4A to 4C were manufactured using a silicon alloy or a silicon compound manufactured as follows as the negative electrode active material. Batteries 4A to 4C were produced in the same manner as in Example 1 except that the negative electrodes 4A to 4C were used. As the metal element M other than silicon contained in the silicon alloy, Ti (negative electrode 4A) or Cu (negative electrode 4B) that does not form an alloy with lithium was used. Moreover, the silicon compound (negative electrode 4C) contained nitrogen as an element other than silicon.

<I> Negative electrode 4A
In the formation of the active material layer to the target, a mixture of Si powder (Co. Kojundo Chemical Laboratory, Ltd.) and TiSi 2 powder (Co. Kojundo Chemical Laboratory) (Si: TiSi 2 = 3: 1 (Molar ratio)). The angle α formed between the fixing base and the horizontal plane was set to 60 °, and the deposition time was set to 25 minutes. The flow rate of oxygen gas was set to 0 sccm. A negative electrode 4A was produced in the same manner as in Example 1 except for the above.
Elements contained in the obtained active material layer were quantified by fluorescent X-ray spectroscopy. As a result, the composition of the formed silicon alloy was SiTi 0.2 .

<Ii> Negative electrode 4B
In the formation of the negative electrode active material layer, a mixture of Si powder (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and Cu powder (manufactured by Kojundo Chemical Laboratory Co., Ltd.) (Si: Cu = 5: 1 ( Molar ratio)) was used. The angle α formed between the fixing base and the horizontal plane was set to 60 °, and the deposition time was set to 25 minutes. The flow rate of oxygen gas was set to 0 sccm. A negative electrode 4B was produced in the same manner as in Example 1 except for the above.
Elements contained in the obtained active material layer were quantified by fluorescent X-ray spectroscopy. As a result, the composition of the silicon alloy was SiCu 0.2 .

<Iii> Negative electrode 4C
In forming the negative electrode active material layer, a silicon single crystal (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was used as a target. Nitrogen gas was introduced into the chamber instead of oxygen gas. The acceleration voltage of the electron beam irradiated to the target was set to -8 kV, and the emission was set to 300 mA. The angle α formed between the fixed base and the horizontal plane was set to 60 °, and the deposition time was set to 40 minutes. A negative electrode 4C was produced in the same manner as in Example 1 except for the above.
Nitrogen gas having a purity of 99.7% (manufactured by Nippon Oxygen Co., Ltd.) was used as the nitrogen gas, and the nitrogen gas flow rate was set to 20 sccm. Further, an electron beam irradiation device was installed in the vicinity of the nozzle to convert nitrogen gas into plasma. In the electron beam irradiation apparatus, the acceleration voltage was set to -4 kV and the emission was set to 20 mA.
Elements contained in the obtained active material layer were quantified by fluorescent X-ray spectroscopy. As a result, the composition of the compound containing silicon and nitrogen was SiN 0.2 .

In the negative electrodes 4A to 4C, the height of the protrusions was 8 μm, the size of the protrusions was 10 μm, and the interval between adjacent protrusions was 20 μm.
Moreover, the porosity of the negative electrode active material layer in each of the negative electrodes 4A to 4C was 40%.

  The capacity maintenance rates of the batteries 4A to 4C were measured in the same manner as in Example 1. The results are shown in Table 7.

From the result of the battery 4A, it can be seen that even when an alloy containing silicon and titanium is used as the active material, an excellent capacity retention rate can be obtained. In addition, it can be seen from the results of the battery 4B that an excellent capacity retention ratio can be obtained even when an alloy containing silicon and copper is used as the active material.
From the result of the battery 4C, it can be seen that even when a compound containing silicon and nitrogen is used as an active material, an excellent capacity retention rate can be obtained.

Example 5
Negative electrodes 5A and 5B were produced in the same manner as in Example 1 except that the negative electrode active material layer was formed as described below. In the active material layer, metallic lithium was deposited in the same manner as in Example 1.
Batteries 5A and 5B were produced in the same manner as in Example 1 except that the negative electrodes 5A and 5B were used.

<I> Negative electrode 5A
When forming the protrusions, a resin mask in which rhombus dots 101 are arranged in a staggered pattern as shown in FIG. 10 was used. In the mask shown in FIG. 10, the long axis W a of the rhombus dots is 20 μm, and the short axis W b of the rhombus dots is 10 μm. The distance l a between two rhombus dots adjacent in the major axis W a direction was 20 μm, and the distance l b between two rhombus dots adjacent in the minor axis W b direction was 18 μm. That is, the spacing of the protrusions adjacent in the long axis W a direction (distance between the center axis) is 40 [mu] m, interval of protrusions adjacent in the minor axis W b direction (distance between the center axis) at 28μm there were. Further, the interval (distance between the central axes) Lc between the protrusions adjacent in the oblique direction was 24 μm.
Using this resin mask, in the same manner as in Example 1, a negative electrode current collector 5A having rhombic protrusions was produced. The height of the protrusion was 6 μm.

A negative electrode active material layer containing columnar particles as shown in FIG. 5 was formed using the negative electrode current collector 5A and using the vapor deposition apparatus shown in FIG. Each grain layer was formed by oblique vapor deposition.
Specifically, the negative electrode current collector was fixed to the fixing base 71. The fixing base 71 was inclined so as to form an angle γ of 60 ° with the horizontal plane (position A).

  The acceleration voltage of the electron beam irradiated to the silicon simple substance which is the target 45 was set to -8 kV, and the emission was set to 500 mA. The flow rate of oxygen gas released from the nozzle was 80 sccm. Silicon and oxygen were deposited on the current collector installed on the fixed base 71 to form the first grain layer 50a on the protrusion. The deposition time was set at 2 minutes 30 seconds. Here, the direction in which the growth direction of the first grain layer 50a is projected onto the surface of the current collector is the direction of the arrow 102 (first direction).

  Next, as shown in FIG. 7, the fixing base 71 was inclined to form an angle of 120 ° (that is, (180−γ) °) with respect to the horizontal plane (position B). A second particle layer 50b was formed on the first particle layer 50a under the same conditions as in the case of the first particle layer. Here, the direction in which the growth direction of the second grain layer 50b is projected onto the surface of the current collector is the direction of the arrow 103 (second direction).

  Thus, by changing the position of the fixing base alternately to position A and position B, an active material layer including columnar particles composed of a laminate of eight grain layers as shown in FIG. 5 is formed. did.

The thickness T of the negative electrode active material layer was 16 μm. The amount of oxygen contained in the negative electrode active material layer was quantified by a combustion method. As a result, the composition of the negative electrode active material was SiO 0.5 . When the porosity of the negative electrode active material layer was determined in the same manner as in Example 1, it was 46%.

<Ii> Negative electrode 5B
Except having formed the negative electrode active material layer containing the columnar particle | grains which consisted of the laminated body of 35 granular layers as shown in FIG. 6 as the vapor deposition time of one granular layer was 38 seconds, A negative electrode 5B was obtained.
The thickness T of the negative electrode active material layer was 17 μm. The amount of oxygen contained in the negative electrode active material layer was quantified by a combustion method. As a result, the composition of the negative electrode active material was SiO 0.5 . When the porosity of the negative electrode active material layer was determined in the same manner as in Example 1, it was 48%.

  Note that the direction of the arrow 102 (first direction) and the direction of the arrow 103 (second direction) are opposite to each other.

  The capacity maintenance rates of the batteries 5A and 5B were measured in the same manner as in Example 1. Further, the negative electrodes 5A and 5B after 100 cycles were visually observed. The results are summarized in Table 8.

  Even when the negative electrode active material layer includes columnar particles composed of a plurality of portions formed by oblique vapor deposition, the generation of wrinkles was suppressed as in the case of the battery 1A of Example 1, and excellent cycle characteristics were exhibited. It is considered that this is because a space can be formed around the columnar particles, and the collision with the adjacent columnar particles can be avoided by letting the expansion of the active material escape to the space.

  Furthermore, the capacity maintenance rates of the batteries 5A and 5B were improved compared to the capacity maintenance rate of the battery 1A. In the case of columnar particles in which the growth direction produced in this example is parallel to the normal direction of the surface of the current collector, the interface stress generated during expansion is caused by the growth direction being the normal direction of the current collector surface. It can be suppressed lower than the columnar particles that are inclined with respect to. For this reason, even if the thickness of the active material layer is large, the generation of wrinkles in the current collector is suppressed, and the capacity retention rate is considered to be improved.

  In the present invention, the surface of the current collector is provided with a protrusion that is easily plastically deformed and easily follows the expansion of the active material. Therefore, according to the present invention, a lithium secondary battery having a high capacity and excellent cycle characteristics can be easily provided. Such a lithium secondary battery can be used, for example, as a power source for portable electronic devices.

It is a longitudinal section showing an electrode plate concerning one embodiment of the present invention roughly. It is a longitudinal cross-sectional view which shows roughly an example of the electrical power collector which provided the projection part on the surface. It is a longitudinal cross-sectional view which shows schematically another example of the electrical power collector which provided the projection part on the surface. It is the schematic which shows an example of the manufacturing apparatus used in order to form an active material layer. It is a longitudinal cross-sectional view which shows schematically the columnar particle contained in the active material layer of the electrode plate which concerns on another embodiment of this invention. It is a longitudinal cross-sectional view which shows schematically the columnar particle contained in the active material layer of the electrode plate which concerns on another embodiment of this invention. It is the schematic which shows another example of the manufacturing apparatus used in order to form an active material layer. 1 is a longitudinal sectional view schematically showing a lithium secondary battery according to an embodiment of the present invention. It is the schematic of the apparatus for providing a projection part in the electrical power collector used by the comparative example and the reference example. 10 is a top view schematically showing a current collector used in Example 5. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrode plate 10, 30 Current collector 11, 31 Base material 12, 32 Protrusion part 20 Active material layer 21 Columnar particle 40, 70 Deposition apparatus 41 Chamber 42, 71 Fixing base 43 Nozzle 44 Gas pipe 45 Target 50, 60 Columnar particle 50a, 50b, 50c, 50d, 50e, 50f, 50g, 50h Granule layer 61 First grain layer 62 Second grain layer 80 Battery 81 Positive electrode 81a Positive electrode current collector 81b Positive electrode active material layer 82 Negative electrode 82a Negative electrode current collector 82b Negative electrode active material layer 83 Separator 84 Battery case 85 Positive electrode lead 86 Negative electrode lead 87 Sealing material 91 Processing roll 92 Backup roll 93 Base material 101 Diamond dot

Claims (11)

  1. A current collector including a base material and a plurality of protrusions supported on the base material, and an active material layer supported on the current collector,
    The protrusion is a battery electrode plate including a conductive material that is more easily plastically deformed than the base material.
  2.   The battery electrode plate according to claim 1, wherein the protrusion has a height of 1 to 15 μm.
  3.   The battery electrode plate according to claim 1 or 2, wherein the base material contains at least one selected from the group consisting of nickel foil, stainless steel foil, and copper foil.
  4.   The battery electrode plate according to claim 3, wherein the copper foil contains at least one element selected from the group consisting of Ni, Si, Sn, Be, Co, Ti, Fe, and Zr.
  5.   The battery electrode plate according to claim 1, wherein the protrusion includes copper having a purity of 99.9% by weight or more.
  6.   The battery electrode plate according to claim 1, wherein the active material layer includes a plurality of columnar particles, and the columnar particles are supported on the protrusions.
  7.   The battery electrode plate according to claim 6, wherein at least a part of the columnar particles are inclined with respect to a normal direction of a surface of the current collector.
  8.   The battery according to claim 7, wherein the columnar particles include a laminate of a plurality of grain layers, and a growth direction of the plurality of grain layers is inclined with respect to a normal direction of a surface of the current collector. Electrode plate.
  9.   The battery electrode plate according to claim 8, wherein a growth direction of the plurality of grain layers is alternately inclined in a first direction and a second direction with respect to a normal direction of a surface of the current collector.
  10.   The battery electrode plate according to claim 1, wherein the protrusion is formed by a plating method, a vapor deposition method, a sputtering method, or a sintering method.
  11.   A positive electrode capable of occluding and releasing lithium ions, and a negative electrode. The electrode plate according to any one of claims 1 to 10, a separator disposed between the positive electrode and the negative electrode, and lithium ion conductivity. A lithium secondary battery comprising an electrolyte.
JP2007271580A 2006-10-26 2007-10-18 Electrode plate for battery and lithium secondary battery including the same Pending JP2008135376A (en)

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