JP2007141605A - Anode and battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anode restrained from collapse of shape, capable of improving characteristics, and a battery using the same. <P>SOLUTION: An electrode reaction part of the anode 12 is supported by an anode current collector having three dimensional structure. The electrode reaction part contains anode activator containing Sn and first elements (Zn, Al, Ag, In, Sb, Pb or the like) other than Sn not electrochemically reacting with Li, and second elements (Co, Cu, Mn, Fe, Ni, Cr or the like) not electrochemically reacting with Li. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a negative electrode containing tin (Sn) as a constituent element, and a battery using the same.

  2. Description of the Related Art In recent years, as mobile devices have higher performance and more functions, or for driving electric vehicles or the like, there is a strong demand for higher capacity and higher output of secondary batteries that are power sources thereof. There is a lithium secondary battery as a secondary battery that meets this requirement. However, when lithium cobaltate is used for the positive electrode and graphite is used for the negative electrode, which is a typical form of the present lithium secondary battery, the battery capacity is in a saturated state, and it is extremely difficult to increase the capacity significantly. . Therefore, the use of metallic lithium (Li) for the negative electrode has been studied for a long time. However, in order to put this negative electrode into practical use, it is necessary to improve the precipitation and dissolution efficiency of lithium and control the dendrite-like precipitation form. is there.

On the other hand, recently, a high capacity negative electrode using tin or the like has been actively studied. However, when these negative electrodes are repeatedly charged and discharged, they are pulverized and refined by vigorous expansion and contraction of the active material, current collection is reduced, or decomposition reaction of the electrolyte is promoted due to an increase in surface area, The cycle characteristics were extremely poor. Thus, it has been proposed to improve the characteristics by using a metal nonwoven fabric having a three-dimensional structure for the negative electrode current collector (see, for example, Patent Document 1).
JP 2003-308831 A

  However, even when a negative electrode current collector having a three-dimensional structure is used, there is a problem that the expansion and contraction of the active material due to charge and discharge cannot be suppressed, and the characteristics are deteriorated due to the shape collapse. In particular, when the cycle is repeated and then left in a high temperature state or when discharge is performed at a high current value, the characteristics are significantly deteriorated, and improvement has been demanded.

  The present invention has been made in view of such problems, and an object thereof is to provide a negative electrode capable of suppressing shape collapse and improving characteristics and a battery using the same.

  The negative electrode according to the present invention comprises a negative electrode current collector having a three-dimensional structure, tin, a first element that can electrochemically react with lithium other than tin, and a second element that does not electrochemically react with lithium. Including an electrode reaction part.

  A battery according to the present invention includes an electrolyte together with a positive electrode and a negative electrode, the negative electrode has a negative electrode current collector and an electrode reaction part, the negative electrode current collector has a three-dimensional structure, The reaction part includes tin, a first element that can electrochemically react with lithium other than tin, and a second element that does not electrochemically react with lithium.

  According to the negative electrode of the present invention, since the negative electrode current collector having a three-dimensional structure is used and the electrode reaction part including tin, the first element, and the second element is provided, the electrode reaction part expands and contracts. Moreover, while being able to improve adhesiveness with a negative electrode electrical power collector, shape collapse can be suppressed. Therefore, according to the battery of the present invention using this negative electrode, the current collecting property of the negative electrode can be secured, and the decomposition reaction of the electrolyte accompanying the shape collapse of the electrode reaction part can be suppressed. Therefore, excellent characteristics can be obtained even when used under severe conditions such as leaving in a high temperature state or discharging at a high current value.

  In particular, the first element may include at least one selected from the group consisting of zinc (Zn), aluminum (Al), silver (Ag), indium (In), antimony (Sb), and lead (Pb). For example, the second element includes at least one selected from the group consisting of cobalt (Co), copper (Cu), manganese (Mn), iron (Fe), nickel (Ni), and chromium (Cr). If so, a higher effect can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  A negative electrode according to an embodiment of the present invention includes a negative electrode current collector and an electrode reaction part supported by the negative electrode current collector. The negative electrode current collector is made of, for example, copper, nickel, titanium (Ti), stainless steel, or a metal material having low reactivity with lithium including at least one of them, and has a three-dimensional structure. . This is because, by using a three-dimensional structure, the contact area between the electrode reaction part and the negative electrode current collector can be increased and the adhesion can be improved. The three-dimensional structure has a network structure such as a foam represented by foam metal, and the voids included may be continuously connected or separated. In addition, what has a three-dimensional structure includes, for example, one obtained by processing a fiber such as a woven fabric or a non-woven fabric, or one obtained by forming a three-dimensional structure by plating. Moreover, as what processed the fiber, what processed the metal fiber and what formed the metal film on the surface of the textile fabric or nonwoven fabric which processed the organic fiber may be used.

  The electrode reaction part contains, as constituent elements, a negative electrode active material containing tin, a first element that can electrochemically react with lithium other than tin, and a second element that does not electrochemically react with lithium. Yes. Thus, by including the 1st element in which an expansion coefficient differs from tin, and the 2nd element which does not react with lithium, shape collapse by expansion contraction at the time of occlusion / release of lithium can be suppressed. Examples of the first element include zinc, aluminum, silver, indium, antimony, and lead. One type may be used, but two or more types may be included. Examples of the second element include cobalt, copper, manganese, iron, nickel, and chromium. One type may be used, or two or more types may be included. The content of these in the electrode reaction part is that tin is 40 atomic% to 90 atomic%, the first element is 5 atomic% to 40 atomic%, and the fifth element is 2 atomic% to 40 atomic%. preferable. This is because, when the contents of the first element and the second element are small, shape collapse cannot be sufficiently suppressed, and when the contents are large, the content of tin is reduced and the capacity is reduced.

  The electrode reaction part may exist in the void inside the negative electrode current collector, may exist by forming a layer on the negative electrode current collector, or may exist in both of them. Moreover, it is preferable that the constituent element of the negative electrode current collector is diffused in at least a part of the electrode reaction part. It is because shape collapse of the electrode reaction part can be further suppressed.

  The negative electrode active material contained in the electrode reaction part may be either particulate or non-particulate, but when a particulate material is used, the average particle diameter of the negative electrode active material particles is 0.1 μm or more. Preferably, it is more preferably 30 μm or less. This is because if the average particle size is too small, the surface area increases and the decomposition reaction of the electrolyte increases, and if it is too large, the shape collapses easily due to expansion and contraction. Moreover, it is preferable that the negative electrode active material particles are fused to each other at least partially. This is because shape collapse due to expansion and contraction can be suppressed.

  Furthermore, when using negative electrode active material particles, in addition to the negative electrode active material particles, other materials such as a conductive material or a binder may be contained as required. The conductive material is not particularly limited, and a conductive material that is chemically stable in the charge / discharge potential region and excellent in electron conductivity is preferable. The binder is not particularly limited, and for example, a thermoplastic resin or a thermosetting resin such as polyvinylidene fluoride, polytetrafluoroethylene, or a copolymer of tetrafluoroethylene and hexafluoropropylene is used. it can. In addition to the negative electrode active material particles, particles of a simple substance, an alloy, or a compound containing the first element or the second element described above may be included.

  For example, the negative electrode is formed by dispersing the negative electrode active material particles in a dispersion medium and applying or spraying the negative electrode current collector having a three-dimensional structure, and then removing the dispersion medium to form an electrode reaction part. It can produce by doing. At that time, other materials such as a conductive material or a binder may be dispersed in a dispersion medium and attached together with the negative electrode active material particles as necessary. In addition, for example, it is preferable to perform heat treatment after removing the dispersion medium to fuse the negative electrode active material particles with each other and to diffuse the constituent elements of the negative electrode current collector into the negative electrode active material particles.

  Further, the negative electrode is formed by directly or physically depositing a negative electrode active material on a negative electrode current collector having a three-dimensional structure by a vapor phase method, a liquid phase method or a thermal spraying method to form an electrode reaction part. You may produce by. Also in this case, it is preferable to diffuse the constituent elements of the negative electrode current collector in the electrode reaction section while causing the constituent elements of the electrode reaction section to mutually diffuse by performing heat treatment after depositing the negative electrode active material.

  This negative electrode is used for a secondary battery as follows, for example.

  FIG. 1 shows the configuration of the secondary battery. The secondary battery is a so-called coin-type battery, in which a negative electrode 12 accommodated in an exterior cup 11 and a positive electrode 14 accommodated in an exterior can 13 are stacked via a separator 15. is there. The peripheral portions of the outer cup 11 and the outer can 13 are sealed by caulking through an insulating gasket 16. The exterior cup 11 and the exterior can 13 are made of, for example, a metal such as stainless steel or aluminum.

  The negative electrode 12 has the structure described above, and the positive electrode 14 includes, for example, a positive electrode current collector 14A and a positive electrode active material layer 14B provided on the positive electrode current collector 14A. The positive electrode current collector 14A is made of, for example, aluminum, nickel, stainless steel, or the like.

The positive electrode active material layer 14B includes, for example, any one or more of positive electrode materials capable of inserting and extracting lithium as a positive electrode active material, and a conductive agent such as a carbon material and the like as necessary. A binder such as polyvinylidene fluoride may be included. As the positive electrode material capable of inserting and extracting lithium, for example, a lithium-containing metal composite oxide represented by the general formula Li _x MIO ₂ is preferable. This is because by including this, the capacity can be increased. MI is one or more transition metals, and for example, at least one of the group consisting of cobalt, nickel and manganese is preferable. x varies depending on the charge / discharge state of the battery and is usually a value in the range of 0.05 ≦ x ≦ 1.10. Specific examples of such a lithium-containing metal composite oxide include LiCoO _{2 and} LiNiO ₂ .

  The separator 15 separates the negative electrode 12 and the positive electrode 14 and allows lithium ions to pass while preventing a short circuit of current due to contact between both electrodes, and is made of, for example, polyethylene or polypropylene.

  The separator 15 is impregnated with an electrolytic solution that is a liquid electrolyte. This electrolytic solution contains, for example, a solvent and a lithium salt that is an electrolyte salt dissolved in this solvent, and may contain various additives as necessary. It is preferable to use the electrolytic solution in this way because high ionic conductivity can be obtained. Examples of the solvent include organic solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. Any 1 type may be used for a solvent and 2 or more types may be mixed and used for it.

Examples of the lithium salt include LiPF _{6 and} LiClO ₄ . Any one lithium salt may be used, or two or more lithium salts may be mixed and used.

  This secondary battery can be manufactured, for example, by laminating the positive electrode 14, the separator 15 impregnated with the electrolyte, and the negative electrode 12, placing them in the outer can 13 and the outer cup 11, and caulking them. it can.

  In this secondary battery, when charged, for example, lithium ions are released from the positive electrode 14 and inserted in the negative electrode 12 through the electrolytic solution. When the discharge is performed, for example, lithium ions are released from the negative electrode 12 and inserted in the positive electrode 14 through the electrolytic solution. In that case, since the negative electrode 12 supported the electrode reaction part containing tin, the 1st element, and the 2nd element with the negative electrode collector which has a three-dimensional structure, an electrode reaction part becomes large with charging / discharging. Even if it expands and contracts, shape collapse is suppressed.

  The negative electrode according to the present embodiment may be used for a secondary battery as follows.

  FIG. 2 is an exploded view of the secondary battery. In this secondary battery, the wound electrode body 20 to which the leads 21 and 22 are attached is housed in a film-like exterior member 31 and can be reduced in size, weight, and thickness. The leads 21 and 22 are led out from the inside of the exterior member 31 to the outside, for example, in the same direction. The leads 21 and 22 are made of a metal material such as aluminum, copper, nickel, or stainless steel, respectively, and have a thin plate shape or a mesh shape, respectively.

  The exterior member 31 is made of, for example, a rectangular aluminum laminated film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order. The exterior member 31 is disposed, for example, so that the polyethylene film side and the electrode winding body 20 face each other, and the outer edge portions are in close contact with each other by fusion bonding or an adhesive. An adhesion film 32 for preventing the entry of outside air is inserted between the exterior member 30 and the leads 21 and 22. The adhesion film 32 is made of a material having adhesion to the leads 21 and 22, for example, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, or modified polypropylene.

  The exterior member 30 may be made of a laminated film having another structure, a polymer film such as polypropylene, or a metal film instead of the above-described aluminum laminated film.

  FIG. 3 shows a cross-sectional structure taken along line II of the electrode winding body 20 shown in FIG. The electrode winding body 20 is obtained by laminating a negative electrode 23 and a positive electrode 24 via a separator 25 and an electrolyte layer 26 and winding them, and the outermost periphery is protected by a protective tape 27.

  The negative electrode 23 has the structure described above, and the positive electrode 24 has, for example, a structure in which the positive electrode active material layer 24B is provided on one surface or both surfaces of the positive electrode current collector 24A. The configurations of the positive electrode current collector 24A, the positive electrode active material layer 24B, and the separator 25 are the same as those of the positive electrode current collector 14A, the positive electrode active material layer 14B, and the separator 15 described above.

  The electrolyte layer 26 is constituted by a so-called gel electrolyte in which an electrolytic solution is held by a polymer compound. The configuration of the electrolytic solution (that is, the solvent, the electrolyte salt, and the like) is the same as that of the coin-type secondary battery shown in FIG. As the polymer material, for example, a polymer containing vinylidene fluoride is preferably exemplified. This is because the redox stability is high. Examples of the polymer compound include those formed by polymerizing a polymerizable compound.

  This secondary battery can be manufactured, for example, as follows.

  First, after preparing the negative electrode 23 and the positive electrode 24, the electrolyte layer 26 in which the electrolytic solution is held in the polymer compound is formed on the negative electrode 23 and the positive electrode 24, respectively, and the leads 21 and 22 are attached. Next, the negative electrode 23 and the positive electrode 24 are laminated via the separator 25 to form a laminated body, and then the laminated body is wound in the longitudinal direction, and the protective tape 27 is adhered to the outermost peripheral portion to bond the wound electrode body 20. Form. After that, for example, the electrode winding body 20 is sandwiched between the exterior members 31, and the outer edges of the exterior members 31 are in close contact with each other by thermal fusion or the like and sealed. Thereby, the secondary battery shown in FIGS. 2 and 3 is completed.

  The electrolyte layer 26 may be formed as follows. For example, an electrolyte composition containing a polymerizable compound and an electrolytic solution is applied to the negative electrode 23 and the positive electrode 24, wound through a separator 25 and sealed in the exterior member 31, and then the polymerizable compound is polymerized. Alternatively, the negative electrode 23 and the positive electrode 24 may be wound around the separator 25 and sealed in the exterior member 31, and then the polymerizable compound and the electrolyte may be contained in the exterior member 31. You may make it form by inject | pouring the composition for electrolyte containing and polymerizing a polymeric compound.

  The operation of this secondary battery is the same as that of the coin-type secondary battery shown in FIG.

  As described above, according to the present embodiment, the electrode reaction part containing tin, the first element, and the second element is supported by the negative electrode current collector having a three-dimensional structure. Even if the reaction part expands and contracts, the adhesion to the negative electrode current collector can be improved and the shape collapse can be suppressed. Therefore, the current collecting property of the negative electrodes 12 and 23 can be ensured, and the decomposition reaction of the electrolyte accompanying the shape collapse of the electrode reaction part can be suppressed. Therefore, excellent characteristics can be obtained even when used under severe conditions such as leaving in a high temperature state or discharging at a high current value.

  Further, specific embodiments of the present invention will be described in detail with reference to the drawings.

(Examples 1-1 to 1-6)
A coin-type secondary battery as shown in FIG. 1 was produced. First, negative electrode active material particles made of an alloy containing tin, a first element, and a second atom were produced by an instantaneous vapor phase generation method using plasma. Specifically, the raw material metal is supplied together with the carrier gas into the tube in which the high-frequency thermal plasma is generated, and the metal is instantaneously melted or vaporized by passing through the plasma part, and then cooled and solidified. Was synthesized. At that time, the first element was changed to zinc, aluminum, silver, indium, antimony, or lead in Examples 1-1 to 1-6, and the second element was cobalt, copper in Examples 1-1 to 1-6. , Manganese, iron, nickel or chromium. The ratios of tin, the first element, and the second element were 80 atomic% tin, 10 atomic% of the first element, and 10 atomic% of the second element. The composition of the synthesized negative electrode active material particles was evaluated by ICP (Inductively Coupled Plasma) emission analysis. Next, the average particle diameter of the synthesized negative electrode active material particles was adjusted to 1 μm with a dry air classifier.

  Subsequently, 75% by mass of the produced negative electrode active material particles, 10% by mass of artificial graphite powder having an average particle diameter of 6 μm as a conductive material, and 15% by mass of polyvinylidene fluoride as a binder were mixed in a dispersion medium. A slurry was obtained. After that, by using a metal nonwoven fabric made of copper fiber having a fiber diameter of 8 μm, porosity of 70% and thickness of 40 μm as a negative electrode current collector, the negative electrode current collector was filled with the prepared slurry, and the dispersion medium was volatilized. Negative electrode active material particles were adhered. Subsequently, the electrode reaction part was formed by heat-processing this at 200 degreeC for 10 hours in argon atmosphere, and the negative electrode 12 was produced. About the produced negative electrode 12, XPS (X-ray Photoelectron Spectroscopy; X-ray photoelectron spectroscopy), AES (Auger Electron Spectroscopy), SEM (Scanning Electron Microscope), EDX (Energy Dispersive X-) When analyzed by a Ray Spectroscope (energy dispersive X-ray detector) and XRD (X-Ray Diffraction; X-ray diffraction method), at least one of the negative electrode active material particles or the negative electrode active material particles and the negative electrode current collector is at least one by heat treatment. It was confirmed that it was fused in the part. It was also confirmed that the constituent elements of the negative electrode current collector were diffused in at least a part of the negative electrode active material particles.

In addition, 92% by mass of lithium cobaltate (LiCoO ₂ ) powder having an average particle diameter of 5 μm as a positive electrode active material, 3% by mass of carbon black as a conductive material, and 5% by mass of polyvinylidene fluoride as a binder are dispersed. A positive electrode active material layer 14B was formed by applying the mixture to a positive electrode current collector 14A made of an aluminum foil having a thickness of 20 μm, drying, and pressing to form a positive electrode 14. Next, the prepared negative electrode 12 and positive electrode 14 were laminated through a separator 15 made of a polypropylene microporous film having a thickness of 25 μm impregnated with an electrolytic solution, and placed in an outer cup 11 and an outer can 13. Sealed by caulking. As the electrolytic solution, a solution obtained by dissolving LiPF ₆ at 1.0 mol / l in a solvent in which 40% by mass of ethylene carbonate and 60% by mass of dimethyl carbonate were mixed was used.

  As Comparative Examples 1-1 to 1-13 for this example, except that the composition of the negative electrode active material particles was changed as shown in Table 1, other than that was the same as Example 1-1 to 1-6 Thus, negative electrode active material particles and a secondary battery were produced. As Comparative Examples 1-14 and 1-15, the composition of the negative electrode active material particles was changed as shown in Table 1, and a copper foil having a thickness of 25 μm and a surface roughness Ra of 0.5 μm was used for the negative electrode current collector. Except for the above, negative electrode active material particles and secondary batteries were produced in the same manner as in Examples 1-1 to 1-6.

With respect to the fabricated secondary batteries of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-15, the storage characteristics and the high load characteristics were examined. The storage characteristic is that after 30 cycles of charge and discharge are repeated, the charge of the 31st cycle is performed, then the battery is stored in a constant temperature bath at 60 ° C. for 10 days, and the discharge of the 31st cycle and the charge and discharge of the 32nd cycle are performed. The ratio of the discharge capacity at the 32nd cycle (discharge capacity after storage) when the discharge capacity at 30th cycle (discharge capacity before storage) was taken as 100% was determined. At that time, charging is constant current and constant voltage charging under conditions of an upper limit voltage of 4.2 V and a current density of 1 mA / cm ² , and discharging is constant current discharging under conditions of a current density of 1 mA / cm ² and a final voltage of 2.5 V. Went.

In addition, the high load characteristic is a constant current constant voltage charge with an upper limit voltage of 4.2 V and a current density of 1 mA / cm ^{2 and} a constant current discharge with a current density of 1 mA / cm ² and a final voltage of 2.5 V. After charging in the fourth cycle under the same conditions, the discharge in the fourth cycle is performed under the conditions of a current density of 5 mA / cm ² and a final voltage of 2.5 V, and the discharge capacity of the third cycle (current density of 1 mA / cm ^2). ) As 100%, the ratio of the discharge capacity (current density 5 mA / cm ² ) at the fourth cycle was determined. The obtained results are shown in Table 1.

  As shown in Table 1, according to Examples 1-1 to 1-6, both storage characteristics and high load characteristics were higher than those of Comparative Examples 1-1 to 1-15. That is, it is understood that storage characteristics and high load characteristics can be improved by supporting the electrode reaction part containing tin, the first element, and the second element by the negative electrode current collector having a three-dimensional structure. It was.

(Examples 2-1 to 2-5)
Except that the composition of the negative electrode active material particles was changed as shown in Table 2, except that the negative electrode active material particles and the secondary battery were produced in the same manner as in Example 1-1. In Examples 2-1 to 2-5, the first element is zinc, the second element is cobalt, the tin content is 90 atomic% to 40 atomic%, the zinc content is 5 atomic% to 40 atomic%, The cobalt content is changed within the range of 5 atomic% to 40 atomic%. For the fabricated secondary batteries of Examples 2-1 to 2-5, the storage characteristics and the high load characteristics were examined in the same manner as in Example 1-1. The obtained results are shown in Table 2 together with the results of Example 1-1 and Comparative Examples 1-1, 1-2, and 1-8.

  As shown in Table 2, when the contents of the first element and the second element were increased, the storage characteristics and the high load characteristics tended to decrease after being improved. That is, the tin content in the electrode reaction part is 40 atomic% to 90 atomic%, the first element content is 5 atomic% to 40 atomic%, and the second element content is 5 atomic% to 40 atomic%. It turned out that it is more preferable if it is within the following range.

(Example 3-1)
A secondary battery was fabricated in the same manner as in Example 1-1, except that the configuration of the negative electrode 12 was changed. The negative electrode 12 was prepared by depositing zinc on the negative electrode current collector made of the same copper non-woven fabric as in Example 1-1 by plating, and further depositing a tin-cobalt alloy, followed by heat treatment at 200 ° C. for 10 hours in an argon atmosphere. It was produced by performing an electrode reaction part. When the produced negative electrode 12 was analyzed by XPS, AES, SEM, EDX, and XRD, zinc, tin, and cobalt were mutually diffused in the electrode reaction part, and the constituent elements of the negative electrode current collector were found in the electrode reaction part. It was also confirmed that it was spreading.

  Moreover, as Comparative Example 3-1 with respect to Example 3-1, except that a copper foil having a thickness of 25 μm and a surface roughness Ra of 0.5 μm was used for the negative electrode current collector, the others were the same as Example 3-1. A secondary battery was produced. For the fabricated secondary batteries of Example 3-1 and Comparative Example 3-1, the storage characteristics and high load characteristics were examined in the same manner as in Example 1-1. The obtained results are shown in Table 3.

  As shown in Table 3, according to Example 3-1, both storage characteristics and high load characteristics were higher than those of Comparative Example 3-1. That is, the negative electrode active material particles are attached to the negative electrode current collector to form an electrode reaction part, or the negative electrode active material is directly deposited on the negative electrode current collector to form an electrode reaction part. It turns out that it is obtained.

  Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the embodiments and examples, and various modifications can be made. For example, in the above-described embodiments and examples, the case where an electrolytic solution which is a liquid electrolyte or a so-called gel electrolyte is used has been described, but another electrolyte may be used. Examples of other electrolytes include solid electrolytes having ionic conductivity, a mixture of a solid electrolyte and an electrolyte solution, and a mixture of a solid electrolyte and a gel electrolyte.

  As the solid electrolyte, for example, a polymer solid electrolyte in which an electrolyte salt is dispersed in a polymer compound having ion conductivity, or an inorganic solid electrolyte made of ion conductive glass or ionic crystals can be used. Examples of the polymer compound of the solid polymer electrolyte include, for example, an ether polymer compound such as polyethylene oxide or a crosslinked product containing polyethylene oxide, an ester polymer compound such as polymethacrylate, and an acrylate polymer compound. Or can be copolymerized. In addition, as the inorganic solid electrolyte, one containing lithium nitride or lithium phosphate can be used.

  In the above embodiments and examples, a coin type or wound laminate type secondary battery has been described. However, the present invention is not limited to a cylindrical type, a square type, a button type, a thin type, a large size, or a laminated laminate type. The present invention can be similarly applied to a secondary battery having the shape. In addition, the present invention can be applied not only to secondary batteries but also to primary batteries.

It is sectional drawing showing the structure of the secondary battery using the negative electrode which concerns on one embodiment of this invention. It is a partial exploded perspective view showing the structure of the other secondary battery using the negative electrode which concerns on one embodiment of this invention. It is sectional drawing showing the structure along the II line of the secondary battery shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Outer cup, 12, 23 ... Negative electrode, 13 ... Outer can, 14, 24 ... Positive electrode, 14A, 24A ... Positive electrode collector, 14B, 24B ... Positive electrode active material layer, 15, 25 ... Separator, 16 ... Gasket, 20 ... Electrode winding body, 21, 22 ... Lead, 26 ... Electrolyte layer, 27 ... Protective tape, 31 ... Exterior member, 32 ... Adhesion film

Claims (10)

A negative electrode current collector having a three-dimensional structure;
An electrode reaction part including tin (Sn), a first element that can electrochemically react with lithium (Li) other than tin, and a second element that does not electrochemically react with lithium. Negative electrode. The first element includes at least one selected from the group consisting of zinc (Zn), aluminum (Al), silver (Ag), indium (In), antimony (Sb), and lead (Pb). The negative electrode according to claim 1. The second element includes at least one selected from the group consisting of cobalt (Co), copper (Cu), manganese (Mn), iron (Fe), nickel (Ni), and chromium (Cr). The negative electrode according to claim 1. The content of tin in the electrode reaction part is 40 atomic% or more and 90 atomic% or less, the content of the first element is 5 atomic% or more and 40 atomic% or less, and the content of the second element is 5 atomic% or more. It is 40 atomic% or less. The negative electrode of Claim 1 characterized by the above-mentioned.   The negative electrode according to claim 1, wherein constituent elements of the negative electrode current collector are diffused in at least a part of the electrode reaction part. A battery comprising an electrolyte together with a positive electrode and a negative electrode,
The negative electrode has a negative electrode current collector and an electrode reaction part,
The negative electrode current collector has a three-dimensional structure,
The electrode reaction part includes tin (Sn), a first element that can electrochemically react with lithium (Li) other than tin, and a second element that does not electrochemically react with lithium. Battery to play. The first element includes at least one selected from the group consisting of zinc (Zn), aluminum (Al), silver (Ag), indium (In), antimony (Sb), and lead (Pb). The battery according to claim 6. The second element includes at least one selected from the group consisting of cobalt (Co), copper (Cu), manganese (Mn), iron (Fe), nickel (Ni), and chromium (Cr). The battery according to claim 6. The content of tin in the electrode reaction part is 40 atomic% or more and 90 atomic% or less, the content of the first element is 5 atomic% or more and 40 atomic% or less, and the content of the second element is 5 atomic% or more. It is 40 atomic% or less. The battery according to claim 6. The battery according to claim 6, wherein a constituent element of the negative electrode current collector is diffused in at least a part of the electrode reaction part.

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