TW201236249A - Cathode active material for lithium ion secondary battery, cathode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents

Abstract

The present invention provides a cathode active material for lithium ion secondary battery having high capacity, high charging -discharging efficiency, and excellent cycling characteristics. The present invention uses a lithium ion secondary battery formed by coating or forming a cathode active material on a current collector, wherein the cathode active material is characterized by using silicon as an essential component and at least comprising a element A of 0.05 mass % or more, and the ratio of a atomic radius rA of the element A to atomic radius r0 of silicon satisfies a relation |(rA-r0)/r0 ≤ 0.1.

Description

201236249 6. Technical Field of the Invention The present invention relates to an anode active material for a lithium ion secondary battery, a cathode using the same, and a clock ion secondary battery, and particularly relates to a second type In addition, it has a six-charge and discharge efficiency, and it is not peeled off from the current collector even if it is repeatedly charged and discharged, and the negative electrode active material of the sub-secondary battery having excellent cycle characteristics can be realized. m [Prior Art] The ion secondary battery is mainly used in portable machines, and it is required to increase the capacity by miniaturization and multifunction of the use of the machine. However, the negative electrode active material used in the conventional ion secondary battery is a carbon-based material such as di-graphite or natural graphite, and the theoretical capacity is cut. The capacity increase of the value or more cannot be expected. Therefore, it has been proposed that a metal material such as s (S η ) or a negative electrode using the oxide material (for example, the literature) can be used, which is capable of obtaining a high specific capacitance. The material that has been noticed by Shi Xi has shown a very high capacity in the initial number of cycles. 疋 The expansion and contraction of the active material due to repeated charge and discharge causes: t negatively cleavage material falls off from the current collector, so compared with the previous " ', / / tongue material, has poor cycle characteristics and short life. Therefore, it has been proposed to make the surface of the si-based active material == sexual action to alleviate the expansion of the negative active material particles. The life is improved (for example, refer to Patent Document 2). And: The active material of the alloy is also alloyed with arsenic and Fe such as an alloying element (for example, refer to Patent Document 3) 〇^ 4 /49 201236249 The track and the second proposal are proposed - a method of making a negative electrode by forming a thin film on a current collector by a CVD method, a money ore method, a steaming method or a dip. Type negative electrode, compared to the set The coating type|pole which is produced by coating the negative electrode active material and the binder of the same type as the earth (2) and the like can suppress the micronization of the negative electrode active material, and the current collector and the active material can be used. Since the electron conductivity of the negative electrode becomes good, and the 'film which forms a negative electrode active material on the foamed current collector' is proposed, the current collector and the bungee are proposed. The adhesiveness of the active material is maintained at a higher level to ensure the capacity of the battery (for example, refer to Patent Document 4). [PTL 1] Patent Document 专利 Japanese Patent Laid-Open No. Hei 07-29602 Patent Literature 2 JP-2006 [Problems to be Solved by the Invention] However, application of a negative electrode active material, a conductive material, and a viscosity is disclosed in Japanese Laid-Open Patent Publication No. JP-A-2004-71305. In the previous negative electrode in which the slurry-like coating liquid of the material is formed to form the negative electrode active material, the negative electrode active material is bonded to the current collecting system using a bonding material of a resin having low conductivity, in order to Since the internal resistance does not become large, it is necessary to minimize the amount of resin used, so the bonding strength is weak. Therefore, when the volume expansion of Si itself cannot be suppressed, micronization and peeling of the negative electrode active material during charge and discharge are caused. In the case where the negative electrode is cracked or the conductivity between the active materials is lowered, the capacity is lowered, that is, the charge/discharge cycle characteristics are poor, and the life of the secondary battery is 5/49 201236249. The expansion itself is described, but the volume of the material am ☆, 丨❾丨 盥隼 盥隼 余 。. _ 贞 贞 活性 活性 : : : : : : : : : : : : : : : : : : 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈 奈In order to improve the charge and discharge cycle, Si is expected to be a material of the negative electrode active material, and the volume change during electricity is large, and the active material particles containing Si are likely to be cracked, so that the current collector in the particles is easily deteriorated. Shortcomings of short cycle life. In addition, although the electrode characteristics of the above-mentioned thin film type negative electrode are greatly improved, there is a charge and discharge cycle when forming a film of an active material quality which is required for an electronic device such as a personal computer or a mobile phone. The tendency to deteriorate in characteristics and to shorten the life of reusable. Therefore, when the lithium ion secondary battery is used, since it is inevitably necessary to reduce the mass of the active material, the use is limited and it is difficult to widely use it. Further, the invention described in Patent Document 4 uses a foamed current collector to increase the thickness of the electrode, resulting in a decrease in the energy density of the electrode and a decrease in the energy density of the battery. Further, at the time of electrode processing, since the edge portion of the foamed portion of the current collector is easily exposed, it is easy to penetrate the thin separator and cause an internal short circuit. The present invention has been made in view of the above problems, and an object of the invention is to provide a negative electrode active material for a lithium ion secondary battery which can be easily deteriorated even after repeated charge and discharge, and which has a high charge and discharge capacity, and is used 6/49. 201236249 A negative electrode of the negative electrode active material material and a lithium ion secondary battery having a long life and high energy density. [Means for Solving the Problem] In order to achieve the above-mentioned object, the inventors of the present invention have found that the second electrode radius having the same magnitude as Si is introduced by using the negative electrode active material containing cerium (si) as a main component. The element can prevent the crystal lattice or the atom of the negative electrode active material from being deformed too much, and the Li ion having a small ionic radius can be easily and easily formed between the lattice of the active material during charge and discharge. Insertion (charging) and detachment (discharging), and the generation of irreversible irreversible capacity due to residual Li ions due to discharge after charging can be reduced. The present invention is based on such knowledge. That is, the present invention provides the following invention. (1) A negative electrode active material material for a lithium ion secondary battery, which is an active material material used for a negative electrode for a lithium ion secondary battery, characterized in that it contains ruthenium as a main component and contains at least 0.05% by mass or more. The particle of the element A is composed of, and the atomic radius ι· Α of the element A described above satisfies the relationship of |(rA-r〇)/r〇| $ 0.1 with respect to the atomic radius r〇 of the 矽. (2) The negative electrode active material material for a lithium ion secondary battery according to (1), wherein the element A is at least one selected from the group consisting of P, Ci., Mn, Fe, Co, Ni, Cu, and As. element. (3) The negative electrode active material for a lithium ion secondary battery according to (丨), which further contains oxygen or gas. (4) The negative electrode active material material for a lithium ion secondary battery according to (1), wherein the particle-based primary particles have an average particle diameter of 10 nm to 5/zm. (5) A negative electrode for a nonaqueous electrolyte secondary battery, comprising: an active material layer which is on one side of the negative electrode current collector or two 7/49 201236249 surface soil cloth 3 having a negative electrode as in (1) The coating liquid of the active material material is dried. (6) A negative electrode for a secondary battery, characterized in that it has a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode current collector has a surface on the surface: and the film-form negative electrode active material layer It is formed on the surface of the negative electrode ^ electric body, and is mainly composed of seconds and contains at least 0.05, ! The element A above: /, the element a is an element in which the atomic half of the atom a of the element a is opposite to the atomic radius of 矽, which is a relationship of $ Q ]. (7) The negative electrode for a secondary battery of the hybrid of (6), wherein the element a is k at least one element of a group consisting of P Ci, Mn, Fe, Co, Ni, Cu, and As. (8) The negative electrode for an ion secondary battery according to (6), wherein the negative electrode active material layer further contains oxygen or fluorine. (9) The negative electrode for a lithium ion secondary battery according to (5) or (6), wherein the negative electrode current collecting system (4) is provided with an electrolytic roughening treatment on a surface of the copper-formed active material layer The protrusion portion has a rough surface roughness Rz of 1 // m to 6 // m. (10) The negative electrode for an ion secondary battery according to (9), wherein the surface of the aforementioned domain before the electrolytic graining treatment is provided with a surface roughness Rz of the surface of the active material f layer of 0.5 #m~3 // m . (11) A lithium ion secondary battery characterized by having a positive electrode, a negative electrode, and a separator, wherein the positive electrode is occluded and discharged by a rotor; the negative electrode is a negative electrode of (5) or (6); The separator is disposed between the positive electrode and the negative electrode, and the positive electrode, the drain, and the separator are provided in an electrolyte having chain ion conductivity. 8/49 201236249 [Effects of the Invention] According to the present invention, it is possible to obtain a high-capacity lithium ion II which has high capacity and high charge-discharge efficiency and which does not peel off or fall off from the current collector even after repeated charge and discharge. A negative electrode active material of a secondary battery or the like. [Embodiment] [Embodiment for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described in detail based on the drawings. (1. Negative electrode for lithium ion secondary battery according to the first embodiment) First, the negative electrode for a lithium ion secondary battery according to an embodiment of the present invention will be described with reference to the drawings. The lithium ion secondary battery of the present invention has an active material layer 5 on one or both sides of the corpse, .., corpse, and the 电 市 city battery y, and the active material layer 5 is coated with the negative electrode active material 3 and is electrically conductive. The coating liquid of the material 4 and the bonding material 6 is dried and dried. Further, the negative electrode active material 3' of the present invention is characterized by being composed of & green matter having a hetero component structure. (M. Configuration of the negative electrode active material) The embodiment of the negative electrode active material for a clock ion secondary battery of the present invention will be described in detail below. The negative electrode active material for ion-exchanged secondary batteries of the present invention has a particulate heterogeneous or heterogeneous system as a main component, and has a second 70-yield. Since the cutting system easily absorbs the elements of the clock, it has the ability to occlude the chain. Moreover, in the case of (4) having lithium occlusion ability: β 夕 has the advantage of relatively low cost. The relationship of 'the atomic radius _.丨丨7nm)#. The atomic element of element A is 原子 atomic radius |\ and Si-like element, and satisfies 1(1.4-1.0)/1.()1 $〇.丨9/49 201236249 Radius W Si atomic radius 满足The relationship, when the element A has the same good as the S], the fine Si lattice and the si as the main body 'the alizarin A are highly likely to be substituted at the same position as the Si atom of the Si lattice. 'Or it is easy to form a compound surface with Si to exist in a state where the S! lattice is stable. On the other hand, when (5) (5) is greater than 0., the Si _ sub-radius, the atomic radii of too small or too large, will be contained by the Si lattice and Si as the main body. A too large element will invade the inter-lattice position of Si, or cause an empty lattice point to be generated and make the Si && into too large 0$·^ 'X ' too small element due to excess solid solution The excessive diffusion of alloying in a limit causes excessive deformation. This kind of element is not affected by its own influence on Li Xuan's Wei Xue movement, or may cause the intrusion of Si crystal lattice during charging, and L丨 Xuan can not be separated during discharge. There is no (four) ke reverse capacity, so it is not suitable for the negative active material material. Element A is represented by the following Table 1, and can be selected from the group of P, Cr, Mn, Fe C〇, Νι, Cu, Ga, Ge, As, Se, Br! Kind to use on the market. Because these elements A are not combined with Li, or even if the total Li is combined, the amount of occlusion is small, and compared with the dream, it forms an element that does not produce a compound with a large change in blue density. The volume is swollen. Further, m (d) may be finely formed into a compound, and may be present in the form of a monomer or a solid solution. When forming a substance, it is not crystalline or amorphous. 〇 and as element A, it is selected from the group consisting of P, Ο, Mn, Fe, Co, Ni, Cu, As to the illusion element, 吣, Fe, N丨, Cu, As The element of low cost is useful. Further, P and elements other than the core can form a compound of the type 5/49 201236249 or SiM2 with Si, because the effect of suppressing the volume expansion and contraction is high. 11/49 201236249 Table 1 Element atomic radius rA(nm) Ion radius rA, (nm) (rA-r〇) / r〇(rA-r〇)/ r〇Li 0.152 0.078 0.30 -0.33 Si 0.117 0.039 0.00 -0.67 B 0.09 0.02 -0.23 -0.83 C 0.077 <0.02 -0.34 -0.83 N 0.053 0.01-0.2 -0.55 0.71 0 0.061 0.132 -0.48 0.13 F 0.071 0.133 -0.39 0.14 Mg 0.16 0.078 0.37 -0.33 A1 0.143 0.057 0.22 -0.51 P 0.109 0.03-0.04 -0.07 -0.70 S 0.102 0.034 -0.13 -0.71 Cl 0.101 0.181 -0.14 0.55 Ti 0.147 0.064 0.26 -0.45 V 0.132 0.04 0.13 -0.66 Ci. 0.125 0.064 0.07 -0.45 Mn 0.112 0.052 -0.04 -0.56 Fe 0.124 0.087 0.06 -0.26 Co 0.125 0.082 0.07 -0.30 Ni 0.125 0.078 0.07 -0.33 Cu 0.128 0.096 0.09 -0.18 Zn 0.133 0.083 0.14 -0.29 Ga 0.124 0.062 0.06 -0.47 Ge 0.123 0.044 0.05 -0.62 As 0.125 0.069 0.07 -0.41 Se 0.116 0.03-0.04 - 0.01 -0.70 Br 0.114 0.196 -0.03 0.68 Zr 0.162 0.087 0.38 -0.26 Nb 0.143 0.07 0.22 -0.40 Mo 0.136 0.068 0.16 -0.42 Ru 0.133 0.065 0.14 -0.44 Rh 0.134 0.068 0.15 -0.42 Pd 0.137 0.05 0.17 -0.57 Ag 0.144 0.113 0.23 - 0.03 Cd 0.149 0.103 0.27 -0.12 In 0.162 0.091 0.38 -0.22 Sn 0.141 0.074 0.21 -0.37 Sb 0.145 0.09 0.24 -0.23 12/49 201236249 The above element A contains 〇〇5 mass in the particles. /〇 above. When the content of the element (A) is a total of (10) 5% by mass and the content of the car is 0.05% by mass or more, the volume expansion and contraction of the charge and discharge can be effectively suppressed. Although the upper limit of the content of the element A is not more than ο/t ′, the mosquito can be arbitrarily placed in a dry circumference of less than 50 depending on the wicking ability of the broken clock. Since the element a, i.e., (4), is often inferior to the effect of suppressing the expansion and contraction of the volume, it is exemplified by, for example, 30 Å or less, and further 20% by mass or less. The 3rd - I in the present & particle-like system can further contain oxygen or fluorine as the =. Although the atomic radius of Oxygen is small, but the radius rA of the above-mentioned magical, the atomic radius of Si and the atomic radius of Si make mnm) corresponding to the large disk; so that only the Qing silk is produced, and it will not become Li ion intrusion. The volume of the shot changes to make the charge and discharge cycle disperse and make =, the complaint is in the heart A. Further, 'Ag and Cd, although the size of the 10 atomic half-heart of the ion protection is large, the third element of the extremely active material which is suitable for the material is not used because it does not contain the S1·binding compound. When β 7 is negative, oxygen and fluorine can be uniformly contained in the particle portion. Needle=two", the charge and discharge characteristics are maintained high, and the amount of the f-containing compound with the element Α is;; = preferably, the particles of the present invention are 10 (10) to 5 (four) w, with the secondary particles The material of the average particle size of the active material is also the right one. Although the influence of the negative electrode which is the main body of Shi Xi, the Hi θ is the average of the Hi to suppress the volume expansion and contraction, and constitute the negative electrode active material 13 / of the present invention. 49 201236249 $If you use the nanometer level of the 1st recording to the secondary particle level, you can fully exert the effect. Therefore, it is possible to set the active material of an appropriate size depending on the application and various types of =. f. For example, when the average particle size j 10nm is used to form the negative active material, the Li ion conductivity and electron channeling path are shorter, and the collection is good and easy to maintain. In addition, when the particles of the U-meter grade to the 5#m grade are used as the negative electrode active material, the coating liquid having excellent coating properties on the surface of the current collector can be adjusted. 'Thick film is easy and capable In addition, the particle system of the present invention can also be used to make the 2 ^ particle of the ruthenium. In this case, considering the practical thickness of the negative electrode active material layer when the negative electrode is formed, The average particle diameter of the secondary particles is preferably 2 () or less, and is difficult to be about 5 Å / m or less. Further, from the viewpoint of particle treatment, the average particle light is preferably 丨Onm or more. The shape system is not particularly limited, and may be, for example, a substantially spherical shape or a linear body. Since the fine particle system is usually aggregated, the average particle diameter of the particles refers to the average particle diameter of the primary particles. A volume-based median diameter that can be used for electron microscopy (SEMm and dynamic light scattering photometer CDLS). The average particle size can be used to confirm the shape of the hybrid by SEM image, and image analysis is used (for example, Asahi Engineering "Azo" -kun" (registered trademark)) to obtain the particle size or to disperse the particles in a solvent by DLS (for example, 琢 琢 琢 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分 充分The measurement results In addition, although the particle shape is a structural shape in which the degree of rain is developed such as B-fast carbon black (high_struc (4), the average particle diameter is defined by the -sub-particle size, and the average particle diameter can be obtained by the analysis of (10) (4) image 14/49 201236249 Further, the average particle diameter of the secondary particles can also be determined by image analysis of the sem photograph to obtain an average particle diameter. Further, in the present invention, the term "germanium as a main component" means that among the elements constituting the particles, the stone is used. The content of cerium is the most, and the content of cerium is preferably 5% by mass or more, more preferably 70% by mass or more. The second element and the third element are elements other than 矽 among the elements constituting the particles. The group of elements with characteristic effects, called the second element and the third element, has nothing to do with the content of the two. Further, the above negative electrode active material of the present invention may be any of a crystal structure, an α-Ribe, a microcrystalline, an amorphous or a doped state. This is because any alloy form is amorphized by alloying with Li ions during charging. (1-2. Production of negative electrode active material) The method for producing the negative electrode active material of the present invention is not particularly limited, and for example, it can be produced by using various known particle (powder) production methods. Particle size. A hair material composed of nano-sized particles of about ~100 nm. The production of nano-sized particles constituting the material of the negative electrode active material can be exemplified by a gas phase synthesis method. For example, by plasma CVD synthesis, the raw material powder of the ship is heated to a temperature equivalent to 10,000 K in a desired composition, followed by cooling, whereby the negative electrode activity having an average particle diameter of (1) (10): right is produced.

Here, a specific example is a high frequency coil 43 for use in the particle manufacturing equipment. 201236249. The high frequency coil 43 is applied with an alternating current voltage of several MHz from the high frequency power source 45. The preferred frequency is 4 MHz. Further, the high-frequency line is wound, and the outer wall of the upper portion of 43 is a cylindrical double-layered official composed of quartz glass or the like, and cooling water is passed through the gap to prevent the money π from causing the quartz glass to smother and melt, and in the reaction chamber 33. In the upper portion, the raw material powder supply port 35 is provided, and at the same time, a shielding gas supply port 39 is provided. The raw material powder 37 supplied from the raw material powder is supplied to the plasma through the raw material powder supply port 35 simultaneously with the carrier gas 42 (rare gas such as helium or argon). Further, the shield gas 41 is supplied to the reaction chamber 33 through the shield gas supply port 39. Further, the raw material powder supply port 35 does not have to be provided in the upper portion of the plasma 47 as shown in Fig. 2, and the nozzle can be provided in the lateral direction of the plasma 47. Further, the raw material powder supply port 35 may be cooled by using cooling water. Further, the raw material properties of the nano-sized particles supplied to the plasma 47 are not limited to powders, and a slurry-form coating liquid and a gaseous material may be supplied to the raw material powder. The effect of the reaction chamber 3 3 is to maintain the pressure of the plasma reaction portion and to suppress the dispersion of the prepared fine powder. In order to prevent damage caused by the plasma 47, the reaction chamber 33 is also cooled by water. Further, a suction pipe is connected to the side of the reaction chamber 33, and a filter 49 for collecting the synthesized fine powder is provided in the middle of the suction pipe. The suction pipe connecting the reaction chamber 33 and the transition unit 49 is also cooled by cooling water. The pressure in the reaction chamber 33 is adjusted by the suction capacity of the vacuum pump (VP) provided on the downstream side of the filter 49. Since the method for producing nano-sized particles is from bottom to top (b〇tt〇m Up), the plasma is solidified by gas or liquid, and nano-sized particles are precipitated, and the ball is formed at the stage of the droplet. shape. On the other hand, in the top down method, such as the pulverization method and the mechanochemical method, the large particles of the 16/49 201236249 f, the lion's silk (four) of the particles are flat and the shape is different, by the raw material powder. A negative active mixed powder of Si = = energy = can be used. The money is made of _ kind_ powder to constitute the negative electrode active material, and (4) by the way of gas, her alloy county metal supply flow is made up of submicron ~ - micron: inch particle jin . In the case of the production of the negative electrode active material obtained by exposure of the obtained negative electrode active material to oxygen or the right enthalpy, the negative electrode active material material containing 5 as the third element can be produced. When it is made to contain milk, it can be exposed to a heated atmosphere. (3) The effect of the negative electrode active material material) The negative electrode active material of the present invention is composed of particles of element A having at least 3 atomic radii of the same size as sand, in addition to cerium. In the A system, the L 丨 ions which do not cause too much change between the Si crystal lattice cut atoms and the small ion enthalpy are able to be unobstructed and easily interposed during charge and discharge, and the intercalation between the active material lattices is generated ( It is possible to reduce the irreversible capacity caused by the residual of U ions accompanying the discharge after charging, and to charge (discharge). Further, when the lithium is occluded with respect to the lanthanum, the volume expands, and since the element A does not occlude or hardly occludes lithium, the volume change due to expansion and contraction and the liter y&gt;' can provide the cycle characteristics. Negative discharge capacity reduction 17/49 201236249 Extremely active material. Further, by containing fluorine having an ionic radius close to the radius of the si atom as the third element, it is possible to provide a negative electrode active material which has a second life of improved charge and discharge cycle characteristics. The negative electrode active material can be an average particle diameter of 10 nm to 5 mm, and can easily adjust a negative electrode active material having a suitable use. k (]_4. Production of a negative electrode by coating a slurry) In the negative electrode active material for a lithium ion secondary battery, the negative electrode active material of the present invention is temporarily coated with a slurry-like coating liquid having s upper (four), a conductive material, and a bonding material, and is applied to a negative electrode 隼 < water t, for example, bad (four) The above-mentioned day (4) negative electrode active (four) material: material, bonding material, bismuth material, dissolved coating replenishment input ^ 2 kneaded to form a polymer-like coating liquid, and applied to the body to form a negative electrode active material layer Manufactured in / / 电 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性 活性(4) For G~25_ as the standard liquid ==3: It means 'can use the coater of the body shape' and can also be used as a kneading machine, Γ. A coating liquid for a water-based coating liquid such as a mixer or a ball mill In the case of a tackifying material, a rubber can be used as a tackifying material, and a mixture of two or more types of polysaccharides such as hydroxymethyl 201236249 vegan and methyl cellulose can be used. In the case of preparing an organic coating liquid, it is possible to use N-methyl as a bonding material, such as polyvinylidene fluoi'ide (PVdF) or the like. -2-pyrrolidone. The conductive material is selected from the group consisting of at least one conductive material consisting of carbon, copper, tin, zinc, nickel, and silver. It may be carbon, copper, tin, zinc, or nickel. The powder of the silver monomer may be a powder of the respective alloys. For example, a usual carbon black such as furnace black or acetylene black can be used, and particularly when the surface of the negative electrode active material of the present invention is exposed, the surface of the negative electrode active material is lowered. Conductive property is preferable because carbon nanohorn is added as a conductive material. Here, carbon nano angle (CNH) is a structure in which a graphene sheet (gl, aphene sheet) is conical, and in actual form, most The CNH system apex is facing outward The outer diameter of the aggregate of the sea urchin such as sea urchin is about 50 nm to 250 Å, and particularly preferably CNN having an average particle diameter of about 80 nm is used. The average particle diameter of the conductive material also refers to the average particle diameter of the primary particles. In spite of the highly developed structural shape such as acetylene black (AB), the average particle diameter is defined by one particle control and can be imaged by SEM photograph. The average particle diameter can be obtained by analysis. It is also possible to use a granular conductive material and a wire-shaped conductive material. The linear conductive material is a conductive material line which can be used in a granular conductive material. Conductive substances have been cited. The linear conductive material can be a linear material having an outer diameter of 300 nm or less, such as a carbon fiber, a carbon nanotube, a copper nanowire, or a nickel nanowire. By using a linear conductive material, it is easy to maintain electrical connection with the negative electrode active material and the current collector, and the current collecting performance can be improved, and at the same time, the porous film-like material in the porous film is increased, and it is not easy in the negative electrode 19/49 201236249. Cracks are produced. It is considered that, for example, AB or copper powder can be used as the particulate conductive material, and vapor grown carbon fiber (VGCF: Vapor Grown Carbon Fiber) can be used as the linear conductive material. Further, it is also possible to use no linear conductive material, and only a linear conductive material. The length of the linear conductive material is preferably 〇. y m 2 mm. The outer diameter of the conductive material is preferably 4 nm to 100 nm, and preferably 25 nm to 200 nm. When the length of the conductive material is 〇.丨/zm or more, it is sufficient to increase the productivity of the conductive material, and if the length is 2 mm or less, the coating liquid is easily applied. Further, when the outer diameter of the electrically conductive material is thicker than 4 nm, it is easy to synthesize. When the outer diameter is smaller than 100 nm, the coating liquid is easily kneaded. The method of measuring the outer diameter and the length of the conductive material is a bonding material of the 0-bonding material-based resin by image analysis of S EM, and a fluororesin such as polyvinylidene fluxride (PVdF) or the like can be used. A rubber system such as styrene-butadiene-rubber (SBR), or an organic material such as polyimine and acrylic. The coating liquid is applied to the current collector, and for example, the coating liquid can be applied to one surface of the current collector using a coater. As the coater, a general coating device capable of applying a coating liquid to a current collector can be used, for example, a Kokon Coater shown in Fig. 4, a coater using a doctor blade, and a doctor blade coating. Machine, mold coating machine, etc. The current collecting system can be made of a material that is not alloyed with lithium, and for example, a foil composed of at least a metal of a group consisting of free copper, nickel, and stainless steel can be used. These metals may be used singly or in combination. The thickness depends on the application, preferably about ~35//111, and further preferably from about 6 μm to 20 μm. From the viewpoint of the thinness, strength, and electrical conductivity of the foil 20/49 201236249, etc. It is preferable that the copper foil is used. In the negative electrode current collecting system of the present invention, it is preferable to provide a protrusion by performing electrolytic roughening treatment on the surface of the copper pig. The surface roughness Rz of the current collector having the protrusion is It is better to use _ kiss m. Because the negative electrode is live! The biomass material is alloyed with the chain to cause expansion, and the surface of the current collector is subjected to hetero-electrolysis (four) treatment to a surface roughness Rz. When the rough surface shape increases the specific surface area and forms a negative electrode having a small amount of active material per unit area, even if the volume of the two-pole active material changes due to charge and discharge, the negative electrode can be relaxed by the gap between the protrusions. The stress caused by the expansion and contraction of the active material material is improved, and the cycle characteristics are increased. Further, since the surface area is increased, the negative electrode active material layer formed in the body: can be closely attached to the negative electrode. Amount required The surface roughness of the electrichorn cattle roughening treatment is less than the surface area of the second surface area, so the negative electrode that can be carried by the negative electrode is less than 3⁄4, and because of the insufficient capacity per unit area. The electric position is reduced, so the cycle characteristics are also reduced. For example, it is a secret volume/丨丨, a pole, and the formation of a layer of debris f causes a bad shadow of 7 people! The negative collector's utility becomes difficult, but it is not good. ^ The surface of the rabbit Ming _ degree Rz Gu 〇 〇 1_1994 10 points average thick chain. | 面 刖 录 recorded in the metal county surface (electrical mine, no electron renewal, and painting, grinding, etc. The method of surface treatment 隹2\/49 person 201236249 In the present invention, the ideal aspect is formed by performing electrolytic roughening treatment on a metal foil having a surface roughness RZ of 〇.5#m 〜3//m. The metal foil (that is, the untreated foil) before the roughening treatment can be a double-sided glossy foil or a double-sided smooth foil formed by an electrolytic method or a rolling method. The surface roughness Rz is set to 〇5 μm or more. Because the actual roughness is small for two-sided glossy foil or two-sided smooth foil, When it is larger than 3/zm, the variation in roughness after forming the protrusions becomes large, which is not preferable. Further, even if the foil is not treated, the surface roughness Rz is Ι/zm or more, but it is formed when the foil is manufactured. The unevenness also includes gentle unevenness, and the adhesion to the active material layer cannot be surely improved. Therefore, it is not preferable to use the untreated foil directly. It is important to form a concave-convex shape having a complicated shape by roughening. By performing the roughening treatment on the metal foil having the surface roughness in the above range, the projections formed on the current collector are in the same plane, and both the inside and the outside are uniform at the same time, and the negative electrode active material can be displayed. Further, the layer has a good adhesion, and the negative electrode active material layer is less likely to fall off, which contributes to a longer life of the negative electrode and ensures the actual capacity. The electrolytic graining treatment roughens the surface by forming a plating film having a convex shape on the surface of the untreated crucible, and for example, a roughening method by electroplating which is usually used can be used. In other words, a soda-plated copper-plated copper layer is formed on the surface of the foil by a so-called electroplating using a sulfuric acid steel aqueous solution, and then a normal film-like plating (capsule plating) is performed on the granular powder-bonded copper layer. It is possible to form a projection that prevents the particles from falling off. This is preferred because it can control the uniformity of the plating layer and ensure reproducibility and excellent quality management. Further, for example, when the material of the current collector is copper, it is preferable to form a protrusion portion having a complicated shape by plating. A current collector having less variation can be easily formed by using an electrolytic copper foil. 22/49 201236249 In addition to zinc and chromate treatment, the rust-preventing layer can also be formed by mineralizing nickel, such as &quot;:: oxiran coupling agent to form a rust-proof layer. By reading the =::::= and the excess of the components of the negative active material, the reading is performed. On (4), fine _ has protrusions. Electric money: two kinds of impregnation treatment: Week:: by sulphate aqueous solution, etc., and the adhesion is ==; The coating liquid can be uniformly applied to the current collector, and then dried at about L, and can be obtained by adjusting the thickness of the pressure, etc., to obtain a plasma for a secondary ion battery. negative electrode. Roller (1-5. Effect of the negative electrode for a clock-ion secondary battery) According to the present invention, since the negative electrode active material of the present invention is used, it is possible to provide volume expansion when the sample is suppressed and occluded. A high-capacity and long-life negative electrode that eliminates problems such as negative electrode active material (4) silking and _, 贞 线 ' '''''''' According to , , and local, since the surface of the current collector is roughened, the bonding force between the negative electrode active material layer and the current collector is high...the relaxation of the negative electrode active I·bioshell material# can be alleviated. The induced stress 'can also improve the cycle characteristics of the electrode. (2. Negative Electrode for Lithium Ion Secondary Battery of Second Embodiment) (2-A. Configuration of Negative Electrode for Lithium Ion Secondary Battery) First, a clock ion secondary according to an embodiment of the present invention will be described with reference to FIG. The battery is used with a negative electrode. The negative electrode 61 for a lithium ion secondary battery of the present invention has a negative electrode current collector 67 and a film-shaped negative electrode active material layer 63, wherein the negative 23/49 201236249 pole current collector 67 has a portion 65 on the surface; The material layer 63 is formed on the surface of the above-described anode current collector 67. Further, the negative electrode active material layer 63 of the present invention is composed of an ultrafine stone-forming film. In addition, the negative electrode active material layer 6 is used for the negative electrode current collector 67 having a special form.糸4 (2-2. Negative Electrode Active Material Layer) The negative electrode active material _63 of the present invention is a film which is formed into a body on the negative electrode surface, and is mainly used as a main component and at least human A is used as the 27th halogen. Since the cutting system easily absorbs the material element, the negative electrode active material layer also has a high absorbing ability. X, among the elements of the retention ability, the '11 series has the advantage of being relatively low in cost. The halogen A is contained in the negative electrode active material layer in an amount of 5% by mass or more. When the plural element A is contained, the content of the element is made more than or equal to %. The lion's body is shrinking when the content is secretly charged and discharged. The content of the element A is particularly limited to the upper limit. However, it can be arbitrarily determined in a range of less than 50% by mass in consideration of the lithium storage capacity and the like. Since the effect of the volume-dependent shrinkage is obtained in a very small amount compared to the amount of the 丨 element a, for example, 3 G% by mass or less, and further 20% by mass or less can be exemplified. Further, the negative electrode active material layer of the present invention may further contain milk or gas as the third element. Although the oxygen and fluorine_sub-radius are small, as shown in Table 1, the atomic radius of the ion system and the atomic radius of 〇R (0.ii7nm) τ. L is not large, so that it does not cause excessive deformation. It will not become ^Electrical disengagement H can suppress (4) volume change and further increase the life of the charge. The oxygen and gas systems also have an effect of dispersing a part of Li 5 to stabilize the active material. Further, Ag and Cd, 24/49 201236249 Although the ion-like Si is reduced in size, it is difficult to form a composite Mb compound, and the third element is a negative electrode active material. &quot; Moreover, the oxygen and fluorine systems may be uniformly contained in the whole milk of the active material layer, and may, for example, also be partially contained in the surface portion. The content of fluorine is preferably 5% by mass or more in order to maintain high charge and discharge characteristics, and is preferably uff% or less in combination with the content of the element A. The negative electrode active material layer of the present invention is practically required to have a thickness of at least the above, and it is preferable that the thickness of the negative electrode active material layer is about 1 Mm to 6 or less. In addition, in the "Θ", the term "11" as the main component means that the content of _ is at most 1 and is preferably 5% by mass or more, and more preferably 7G. %the above. In addition, the second element and the third element are the elements of the element constituting the particle, and the group of the element group having the special effect is called the second element, the 帛3 element, and the The content does not matter. The above-mentioned negative electrode active material of the present invention may have any of crystal structure, crystal, micro, amorphous or spin-adapted state, because it is alloyed with Li ions during charging, and the crystal form is uniform. The reason for the amorphization is carried out. In addition, the film forming method of the negative electrode active material layer of the present invention is not particularly limited, and for example, a film having the above-described, and the like can be formed by various known film forming methods, and specifically, for example, For example, the method of bismuth ore, ore, CVD, etc. can be used to form a uniform sentence when using these methods. (2-3. Negative current collector) 25/49 201236249 The negative electrode current collector system of the present invention can be used. With the lithium alloy structure, for example, a foil composed of a metal selected from the group consisting of copper, nickel, and stainless steel can be used. These metals may be used singly or as a ruthenium alloy. (4) The viewpoint of thinness, strength, electrical conductivity, etc., is better with steel files. Although the thickness depends on the application, the thickness of the protrusion is preferably as good as the right, and it is preferable to enter about 20em. a / Moreover, the negative electrode current collecting system of the present invention has a projection. The protrusion portion is preferably provided by subjecting the surface of the copper (four) to electrolytic graining treatment. The surface roughness I degree Rz is preferably [&quot;m~6&quot; m. The reason for this is that the negative electrode active material material is alloyed with the chain to cause expansion, so that the surface of the current collecting spoon is 幵y-like, and the surface rough chain shape Rz is a fine rough surface shape of ～6#yang. When a negative electrode having a small amount of active material per unit area is formed, and a volume change of the negative electrode active material layer is caused by charge and discharge, the gap between the protrusions can be used to alleviate the negative substance layer. The stress caused by expansion and contraction, and can improve the cycle characteristics. Further, since the surface area is increased, the negative electrode active material layer formed on the surface of the current collector can be loaded with the amount required for the negative electrode to be satisfactorily adhered. g dog up. When the surface roughness rz of ruthenium is smaller than 丨# m, it is difficult to carry the negative electrode active material layer directly forming a thin film on the current collector without peeling off. Further, even if the negative electrode active material layer of the present invention is used, the surface area of the current collector is not sufficiently large, so that the mass of the negative electrode active material that can be carried becomes insufficient, and since the charge and discharge position per unit area is reduced, The characteristics are also reduced, but it is not good. When the surface roughness Rz is greater than 6 dances, the thickness of the current collector becomes too large. (4) The negative active material 26/49 201236249 is adversely affected, for example, as a cylindrical or quadrilateral axis of the polar coil type. The negative electrode current collector of the primary battery is difficult to be put into practical use, and the surface roughness Rz of the present invention is defined as the ten point average roughness of the industrial standard JIS B0601-1994. = Heavy protrusions can use wet type (electrical ore deposit, chemical etching or electrochemical etching), dry (vapor deposition, material) method, and coarse area of recording and grinding materials on the flat surface of the metal falling surface. The method of reason Y. The present invention is formed by performing electrolytic roughening treatment on a copper foil having a surface texture k of .2. The metal foil (i.e., the untreated foil) before the kneading treatment enables the two-side light or the both sides formed by the rolling method to be smoothly smoothed. = set to 〇.5&quot;m or more because the actual roughness is smaller for the two-side gloss '5' smooth 蝤, and when it is greater than 3', the deviation of the coarse _ degree after forming the protrusion becomes larger. It is not good. Two: the untreated foil also has a rough surface Rz is 丨 _ above == when the concave and convex system formed also contains gentle irregularities, the adhesion of the second system is not improved, so the direct use of untreated, by ' :. It is important to form a concavo-convex system having a complicated shape by roughening: the surface: the embossing is performed on the metal case of the surface roughness in the above range, and the protrusion formed on the current collector is on the same side. In the meantime, the two sides are uniform at the same time, and the negative electrode active material layer can be displayed. The adhesion is good, so that the negative electrode active material layer does not easily fall off, and the monthly b° contributes to the long life of the negative electrode and ensures the actual capacity. . The Λ ό ί 雷 寺 寺 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将 将That is to say, by using the copper sulphate 27/49 201236249 granule powder to order electricity, after forming a granular powdered ore layer on the falling surface, a general film-like shovel is applied on the formation C (capsule plating). ), and can be regulated ^ &amp;Q Bu because the burning Wei can control the uniformity of the money layer and ensure that the material of the brother and the quality of the business is as good as β έ 例如 例如, for example, when collecting electricity Because of the ability to form a collection of complex protrusions by electric ore. By using an electrolytic steel crucible, it is possible to easily form a current collector having a small amount of deviation and zinc and forming a projection, and it is also possible to form an anti-iron layer by plating a nickel-niobium-preventing sub-salt treatment or a shovel coupling agent treatment. . By the rust layer, for example, it is possible to prevent or suppress deterioration caused by a high temperature environment at the time of formation of the negative electrode active material layer at the time of stocking after the production. Further, it is preferable to prevent the component of the current collector and the component of the surfactant active material f from being excessively distributed. Practically, it is known that the main body of the protrusion is formed, which is known to be treated by electroless (4) treatment of a sulfate aqueous solution, substitution plating, or functional surface treatment by gas phase method, rust prevention treatment, and adhesion enhancement. Any of the above treatments is preferred. (2-4. Effect of the negative electrode for a clock-ion secondary battery) When the negative electrode for an ion secondary battery is used, the negative electrode active layer is contained in an atom having the same magnitude as the stone +The diameter of the halogen A 'Element A system does not cause the Li ion with a small ionic radius between the Si lattice or the Shi Xi atom to be charged and discharged at the time of the charge and discharge. The insertion (charging) and the separation of electricity are generated between the cells, and the generation of irreversible capacity caused by the residual of U ions accompanying the discharge after charging can be reduced. Compared with the Shi Xi system, the volume is expanded when the bell is occluded, because the element A does not absorb or is difficult to occlude the clock, so the volume change caused by expansion and contraction and 28/49 201236249, rev vy ι enough to provide the suppression cycle characteristics A negative electrode for an ion secondary battery having a reduced discharge capacity. _, ‘一且’ can provide a negative electrode for a lithium ion secondary battery having improved electric cycle characteristics and battery life by containing a 第 having an ionic radius close to the radius of the Si atom. In addition, it is possible to provide a negative electrode for a lithium ion secondary battery which has a sufficient effect of the negative electrode active material (4) as described above. (3. Configuration of a lithium ion secondary battery), a lithium ion secondary battery according to the embodiment of the present invention, and a positive electrode 13 and a negative electrode, and a separator 15 in which the positive electrode 13 is capable of occluding and discharging lithium ions; the negative &lt;1 is the negative electrode 1 for the above-described clock ion secondary battery of the present invention; and the separator 15 is disposed on the positive electrode 13 and the negative electrode 1 In the electrolyte 17 having lithium ion conductivity, the positive electrode 13, the negative electrode 1, and the separator 15 are provided. (4. Positive electrode) The ruthenium positive electrode can be produced by directly applying a composition of a positive electrode active material to a metal current collector such as an aluminum foil and drying it. The composition of the positive electrode active material can be prepared by mixing a positive electrode active material, a conductive auxiliary agent, a binder, and a solvent. (4-1. Positive Electrode Active Material) As the positive electrode active material, any user can be used, for example, LiCo02, LiMn204, LiMn02, LiNi02, LlC〇i/3Ni1/3Mnl/3〇2. A compound such as LiFeP04. (4-2. Conductive Aid) The conductive auxiliary agent is a powder composed of at least one conductive material composed of carbon, copper, tin, zinc, nickel, silver, or the like, which is composed of at least one of groups 29/49 201236249. It may be a powder of a monomer of carbon, copper 'tin, zinc, nickel, silver, or a powder of a respective alloy. For example, usual carbon black such as furnace black or acetylene black can be used. It is preferred to add a carbon nanohorn as a conductive additive. Here, the carbon nano angle (CNH) refers to a structure in which a thin graphite flake is formed into a conical shape, and in an actual form, an aggregate of a plurality of CNH vertices facing outwards and in a form such as a radial sea urchin The way there is. The outer diameter of the aggregate of CNH such as sea urchin is about 50 nm to 250 ηπι. In particular, it is preferred to use CNH having an average particle diameter of about 8 Å. The average particle diameter of the conductive auxiliary agent means the average particle diameter of the primary particles. In spite of the highly developed structural shape such as B-carbon black (AB), the average particle size is defined by the primary particle size. The particle size measurement system can use the electron microscope (SEM) image information and the volume reference median diameter of the dynamic light scattering photometer (DLS). The average particle size can be confirmed by SEM image in advance, and image analysis can be performed using image analysis (for example, Azo-kun (registered trademark) made by Asahi Kasei ENGINEERING, or particle dispersed in a solvent by DLS (for example, 冢Measurement by electronic DLS_8000) When the fine particles are sufficiently dispersed and do not aggregate, substantially the same measurement results can be obtained by using SEM and DLS. Further, both a particulate conductive auxiliary agent and a linear conductive auxiliary agent may be used. The conductive auxiliary agent-based conductive material may be a conductive material exemplified as a particulate conductive auxiliary agent. The linear conductive auxiliary agent may be a carbon fiber, a carbon nanotube, or a copper nanowire. A linear material having an outer diameter of 300 nm or less, such as a nickel nanowire, can be easily electrically connected to the negative electrode active material and the current collector by using a linear conductive auxiliary agent, thereby improving the current collecting performance while being porous. The film-like negative electrode fibrous material increases, and the negative electrode is not allowed to be cracked at 30/49 201236249. It is considered that, for example, Αβ or steel powder can be used as a granular conductive auxiliary agent' and a vapor-grown carbon fiber (VGCF) is used. : Vapor Grown Carbon Fiber) as a linear conductive additive. It is also possible to add no particulate conductive additive, and only use linear conductive additives. The length of the linear conductive additive is 0.1 Am~2mm. Preferably, the outer diameter of the conductive auxiliary agent is preferably 4 nm to 丨OOOnm, preferably 25 nm to 2 〇〇 nm. If the length of the conductive auxiliary agent is 〇.丨 or more, it is used to enhance the conductive auxiliary agent. The sufficient length of productivity, if the length is 2_ or less, the drug body is easy to apply. X, when the outer diameter of the conductive auxiliary agent is thicker than 4_, it is easy to synthesize, and when the outer diameter is smaller than 100om, the slurry is easily mixed. The method of measuring the outer diameter and length of the conductive additive can be carried out by image analysis of SEM. (4-3. Adhesive) Glue adhesive (binding agent) is a resin adhesive that can be used. A gas-based resin such as polyvinylidene fluoride (PVdF), a rubber system such as styrene-butadiene rubber (sbr), and an organic material such as a poly-imine (PI) and a water-soluble binder. (4-4·Solvent) As a solvent, it is a NHL scale (NMp), water, etc. The content of substances, conductive additives, binders, and solvents is sufficient. It is adjusted appropriately in the case of the sub-battery: the battery is normally adjusted. (4-5. Manufacture of the positive electrode) The machine for adjusting the positive electrode active material adjusted as described above is uniformly applied to the side of the thunder and the tenth column. For example, a coating machine using a doctor blade, a product coated with a current collector, a coater using a doctor blade, a knife coater, and a mold collector system can be selected from the group consisting of copper, nickel, and steel. Group 201236249, composed of one type of metal (4). These systems can be used alone or in combination with each other. The thickness is also dependent on the application, preferably 4&quot;m~35&quot; m, and then 6&quot; It is preferable that m~2Q^(7) is around. After coating the composition of the positive electrode active material, it is dried at about 5 〇 to 5 〇艽

The positive electrode is obtained by drying and adjusting the thickness of the roll. L (5. Separator) As a separator, it has a function of insulating the positive electrode from the negative electrode, and is used as long as it is used in the clock ion II: undercurrent. = If a microporous polyolefin film can be used. (6. Electrolyte) As the electrolyte, various electrolytic solutions and electrolytes having lithium ion conductivity can be used. For example, an organic electrolytic solution (nonaqueous electrolytic solution), an inorganic solid electrolyte, a polymer solid electrolyte, or the like can be used. Specific examples of the solvent of the organic electrolytic solution include carbonic acid such as ethylene carbonate, propyl carbonate, butylene carbonate, diethyl carbonate, dinonyl carbonate, and methyl ethyl carbonate. Ether; ethers such as diethyl ether, dibutyl ether, ethylene glycol didecyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether; benzene Nitrile, acetonitrile, tetrahydrofuran, 2_mercaptotetrahydrofuran, r-butyrolactone, dioxapentane, 4·decyldioxolane, anthracene, fluorenyl-dimercaptocarboxamide, dimercapto An aprotic solvent such as guanamine, dimercaptopurine or nitrobenzene, or a mixed solvent of two or more of these solvents. The electrolyte of the organic electrolyte can be used by LiPF6, UCl〇4,

LiBF4, LiA104, LiAICl4, LiSbF6, LiSCN, LiC Bu LiCF3S〇3,

One or a mixture of two or more kinds of electrolytes composed of lithium salts such as LiCF3C03, LiC4F9S03, and LiN(CF3S02)2 is used. 32/49 201236249 The organic electrolyte is added to the solid electrolyte interface film which is effective on the surface of the negative electrode active material as an additive. It is a good example of the addition of a compound which can be reduced in the molecule when it is charged in an unsaturated medium. For example, ethyl carbonate (VC) and the like. Further, a solid plasma ion conductor can be used instead of the above-mentioned column. For example, a solid polymer = a sub-material impregnated electrolyte which can be used by mixing the above-mentioned salt by polyepoxy firing, polyepoxy firing, or polypolymer can be used. And the processing becomes gelation = and, also, a telluride, a _ compound, a bell oxyacid salt, Y i^iQ4_ui_u〇h, u3j&gt; 〇4_Li4Si〇4, Li2SiS3, a body electrolyte must be S1S2, a vulcanization Material material as inorganic solid (7. Lithium ion secondary battery assembly) (4) A clock ion secondary battery is provided with a separator between the positive electrode and the negative electrode of the present invention to form a battery element. After that, after winding or laminating into a cylindrical or square battery case, an electrolyte is injected to serve as a clock ion secondary battery. η system 'this ringing ion secondary battery cup mAA negative electrode 1 ^ separator 丨 5, and according to the separator - negative electrode - compartment constitutes ::: sequence: layer configuration 'and positive side 〖3 is the inner side of her feng ^ And insert the 匕 into the battery can 9]. Therefore, the positive electrode 13 leads 21 and is connected to the positive electrode terminal 25', and the negative electrode 1 passes through the negative electrode battery can 19 so that the inside of the battery ion secondary battery η can be taken out in the battery can 19 by electric energy. external. Next, after the tank 9 is filled with the electrolyte 17 to cover the electrode group, the sealing body 27 is attached to the upper end (opening) of the battery can 33/49 201236249 19 via a ring-shaped insulating spacer, which is a circular cover plate and The upper positive electrode terminal 25 is formed, and a safety valve mechanism is housed in one of the bowl portions; . (8. Effect of the clock-ion secondary battery of the present invention) The lithium ion secondary battery of the present invention is composed of particles containing Si and a second element, and the Si system has a capacity per unit volume higher than that of carbon; The two elements have an atomic radius of the same size as Si; since the negative active material material which produces an irreversible capacity is used, the capacity of the ion secondary battery is large, and since the particles are difficult to expand and contract in volume: Therefore, the cycle characteristics are good. In addition, the negative electrode for the secondary battery of the present invention, which is capable of alleviating the expansion I (4) of the negative electrode active material f, can be provided by the use of the negative electrode active material layer and the current collector. An excellent and economical lithium ion secondary battery. [Examples] Hereinafter, the present invention will be specifically described using examples and comparative examples. [Examples]: A negative electrode active material was applied to produce a negative (manufacture of a current collector), and a Nc_ws box made of Fuchang Electric Co., Ltd. having a thickness of electrolytic copper, and an Rz of M (4) were used to produce an ore. Electric body. The plating conditions are as follows. (a) roughening of the burnt ore in the copper, 3, sulfuric acid, ton / as the main 2 knives in the electrolyte 'not warmed at the current density of Sichuan, 2 ^ im van _ _ electrolysis Time—When selected, cathodic electrolysis is carried out in advance on the condition of the shape of the surface to be determined. (8) Smooth copper plating (capsule plating) of roughening treatment: The copper foil 34/49 201236249 7〇g/dm3, sulfuric acid 〇〇g/dm3 as a main component and the liquid temperature was maintained at 4 Torr. [In the electrolytic solution, in the range of the current density of 5 to 丨0 A/dm2, the cathode electrolysis is carried out in advance under conditions which are appropriately selected depending on the conditions (a) and the electrolysis time for obtaining the predetermined surface shape. Further, the copper foil is formed by using nickel and zinc to form an inorganic film, and is subjected to chromate treatment using cathodic electrolysis of a well-known aqueous solution to form a film having a thickness of nanometer, and then impregnated with (mercapto) acrylonitrile. An oxygen-based decane coupling agent water; a valley liquid to form each anti-mine treatment layer as a current collector. (Production of Negative Electrode Active Material Material 1) As a negative electrode active material, Si, Si-B, Si-P, Si-Fe, and Si-Ni-based nanosized particles were produced using the plasma cVD apparatus of Fig. 2 . . As the raw material, a suitable powder was prepared using Si powder and B powder having an atomic radius of 〇. 9 nm, P powder having an atomic radius of 0.11 nm, and Fe powder having an atomic radius of 012 ηη 'Ni atom having an atomic radius of 〇.12 nm. The nanosized particles are produced by drying the mixed powder and continuously supplying the carrier gas to the plasma of the Ar gas generated in the reaction chamber. Specifically, after evacuating the reaction chamber using a vacuum pump, Ac gas was introduced and set to 1 atm. This exhaust gas was introduced three times and Ar gas was introduced to exhaust the residual air in the reaction vessel. Subsequently, Ar gas was introduced into the reaction vessel at a flow rate of 13 L/min as a plasma gas, and an alternating voltage was applied to the high-frequency coil to generate high-frequency plasma by a high-frequency electromagnetic field (frequency: 4 MHz). The plate power system at this time is set to 2 kW. The carrier gas system for supplying the raw material powder used an Ar gas having a flow rate of 1.OL/min. The obtained fine powder was subjected to micro-oxidation treatment for preventing dust explosion 12 hours after the production, and then recovered using a filter. (Manufacturing of Negative Electrode Active Material Material 2) 35/49 201236249 Further, an alloy molten metal having a predetermined composition of Si_B or SUP is prepared as a negative electrode active material, and is obtained by micronization by a known atomization method using nitrogen gas. Si-β, Si-P-based micron-sized active material particles. (Production of Negative Electrode Active Material Material 3) The obtained negative electrode active material material is subjected to atmospheric oxidation treatment using a temperature of 18 (TC) to contain oxygen. (Analysis of composition of negative electrode active material) The 2-3 (high-frequency inductively coupled plasma luminescence spectrum) analysis using an aqueous solution in which a material is dissolved is carried out for the quantification of the components, and the result is such that the mass of the entire material is set to 100. The mass ratio of the component is shown in Table 2 as the subcomponent concentration (mass%). (Production of Negative Electrode) For the negative electrode active material prepared as described above, 1% by mass of carbon black was mixed as a conductive material, and internal nitrogen was used. Mixing was carried out in a substituted ball mill. After mixing the mixed powder with polyimine as a bonding material in a ratio of 95:5, NMP (N-methyl-2·pyrrolidone) was added as a solvent and sufficiently The negative electrode coating liquid was kneaded to obtain a thickness of 1 Svm on the current collector, and fired at 300 ° C for 1 minute, and then used to achieve a density of 2 g/cm 3 by using a roll press. The rolling process was carried out, and the punching was performed into a disk shape of 2 cm 2 to obtain a negative electrode. [Examples 1-1 and 1-2] Two kinds of nanometer sizes Si- of different P concentrations synthesized by the above-described plasma method were used. The negative electrode used as the active material of the P particles was used as an evaluation of the electrochemical characteristics as the test 36/49 201236249. [Example 1-3, 丨_4] #实_1 Nit size team oxygen The Si-Po particles were introduced into the test electrode as an active material treatment, and the electrochemical characteristics were evaluated. The negative electrode was formed as [Example 1-5] The oxygenation was carried out by the above-described atomization method. The sputum sputum particles were subjected to the negative electrode of oxygen, and the electrochemical characterization material was evaluated as a test electrode [Example 丨-6], and the negative active material was used as the nanoactive material synthesized by the above-mentioned Wei method. (4) As a § pole _ evaluation of the electrochemistry [Example 1-7] Using the nanometer active material synthesized by the above-mentioned plasma method, 1 particle was used as the property. Evaluation of Electrochemical Specific Examples 1-8, 1-9] The pure and si_Ni particles of Examples 4 to 5 were The e and S1_Nl_〇 particles after the oxidation treatment were used as the active material, and the electrochemical characteristics were evaluated as the test electrode. [Comparative Example 1·1~丨_3] As a comparative example, the system was used as a comparative example. Each of the negative-sized Si monomer particles, the nano-sized particles, and the micro-sized Si-B particles used as an active material material was used as a test electrode for evaluation of electrochemical characteristics. (Evaluation of Electrochemical Characteristics of the Electroplating Electrode) 37/49 201236249 The above-mentioned tantalum film plate is used as the working electrode, lithium metal is used as the counter electrode and the reference electrode, and a mixed solvent of 1 mol of LiPF0 of ethyl carbonate + diethyl carbonate (volume ratio of 1:1) is dissolved. A beaker battery was prepared as an electrolyte. (Electrical Characteristics Evaluation of the Electroplating Electrode) The obtained negative electrode was processed into a disk shape having a diameter of 20 mm and used as a working electrode for evaluation of electrochemical characteristics. Further, lithium metal is used as a mixed solvent of a counter electrode and a reference electrode 'carbonate-extended ethyl ester + diethyl carbonate (volume ratio: 1:1) in which Lipol 6 of 1 mol is dissolved, and these are used as an electrolyte. At the same time, a beaker was placed to prepare an electrochemical evaluation battery. (Evaluation of Electrochemical Characteristics of Shixia Electrode) Subsequently, the battery was evaluated using electrochemical characteristics to evaluate the charge and discharge performance. The process of scanning the potential of the working electrode in the lower (|〇wer) direction (reduction side) is called charging', and the process of scanning the potential of the working electrode in the higher (highei) direction (oxidation side) is called discharging. First, the initial charge and discharge system is 〇丨CA, and the charging system is carried out until 〇2v (at a constant potential until G.G5CA), and the discharge system proceeds to 丨5V. The charge and discharge after the second cycle was charged to G 2CA to G.G2V (at a constant potential of up to 0.05CA). The discharge fine G.2CA was carried out to 1.5V. Evaluation temperature The system 25 C I was evaluated under such conditions, and the capacity conversion rate was obtained from the discharge capacity cycle of the first charge and discharge and the discharge capacity of the fifth ring: domain ring. Also, the capacity retention rate is defined as follows. Heli maintenance rate - (discharge capacity at the 5th cycle / discharge capacity at the first cycle) x] 〇〇 Table 2 shows the capacity retention rate of the test results and the test evaluation results. The capacity shown in the table is the capacity of (f) the unit f amount. 38/49 201236249

However, in Example M~, the active material containing S; (P, Fe, Ni) has a second maintenance ratio, and the capacity after charging and discharging the ring is approximated. The dense matter of the sub-radius material and the actual two. The result of ..., [-..., can be confirmed - the active material shell material preferably contains oxygen molecules. Further, at this time, introduction of an oxygen atom causes an increase in the average particle diameter of the substance m material, which greatly affects the capacity retention rate. On the other hand, when the elemental radius of the comparative example]-2 to 3 is not satisfied with the element (B) which does not satisfy the relationship of 丨(rA-r())/rG丨0.], the capacity dimension of the negative electrode is 39. /49 201236249 The holding rate is greatly reduced. In the present embodiment, the second element of the P, Fe, and Ni materials is used, and oxygen is used as the first active material. The negative electrode active material of the present invention is not limited thereto. As long as at least the atomic radius system satisfies |〇, Α is the U element, :, except for p, and Ni, it is estimated that even if the use case is used, or fluorine is used as the third element, it is possible to obtain this embodiment. Mine (10) Lai as a current collector =, two fruit. Protrusion surface = surface roughness _ the result of the same tendency. According to the present embodiment [Example 2: Production of a negative electrode in a current collector] (Production of a negative electrode for a lithium ion secondary battery), the surface of the current collector obtained by the same method as in Example 1 was opened. The surface of the Si, S, P, Si-As, Si-B, and Si-N phase 6A contains k and a substance layer to produce a negative electrode for a rotor secondary battery. ▲ 'Open, = very active material layer using catalyst chemical vapor growth (CM' installed into ^ 2 conditions below the film. First, the Si film production system using single stone gas as a raw material gas' Further, when the flow rate is 2 Gseem, the current collector temperature is 2 耽, and the medium temperature surface t is used as a basic condition, and the film formation time is appropriately set for 5 weeks according to the thickness of the film. Further, when P is contained as the second element, When the monoterpene is supplied and the phosphine gas is supplied as the material gas, and the flow rate is changed to 1Qs_ or (10). When As is contained as the second element, the supply of the helium gas is supplied as a raw material gas. In the case of B, it is supplied as a raw material gas, and when it contains n, it supplies ammonia gas (1) such as "(7) as a raw material gas. (Manufacture of negative electrode for lithium ion secondary battery 2) When oxygen is added as the third element to the surface of the current collector, the negative electrode active material layer having a composition of Si_P_〇 is formed by reactive sputtering using oxygen-containing Si to produce a lithium ion secondary battery. Negative electrode. Specifically, it is a different oxygen content. i and P substrates are sputtered to form a desired ratio = active material. ' (Production of negative electrode for lithium ion secondary battery 3) The negative electrode obtained by using the Cat-CVD apparatus described above is heated to 180 ° C. The constant temperature bath was subjected to atmospheric oxidation treatment to contain oxygen. [Examples 2-1 to 2-3] The collectors provided with the protrusions were subjected to a Cat-CVD method to change the p content and the thickness to form three types of anode activities. The material layer is used as the negative electrode. [Example 2-4] The current collector provided with the protrusions is formed by using a Cat-CVD method to form a negative electrode active material layer containing Si and P, and is oxidized using a constant temperature bath to contain Si. [Example 2-5] The negative electrode of Example 2-3 was oxidized using a constant temperature bath to form a negative electrode active material layer containing Si, P, and 0 as a negative electrode. [Example 2-6] In the current collector provided with the protrusions, a negative electrode active material layer containing Si, P, and ruthenium is formed as a negative electrode by using a reactive crucible. [Example 2-7] The current collector provided with the protrusions is Formed using Cat-CVD method containing 41/49 201236249

The negative electrode active material layers of Si and As serve as a negative electrode. [Example 2-8] The negative electrode of Example 2-7 was oxidized using a constant temperature bath to form an anode active material layer containing Si, P and ruthenium as a negative electrode. [Example 2-9] A copper foil having a smooth surface different from that of Example 2_ was subjected to a roughening treatment, and a copper box having a projection but having a small surface roughness was formed by a Cat-CVD method. A negative electrode active material layer containing Si and P is used as a negative electrode. [Comparative Example 2-1] A negative electrode active material layer composed of a Si monomer was formed as a negative electrode by a Cat-CVD method on a current collector provided with a projection. [Comparative Example 2-2] A negative electrode active material layer containing Si and B was formed as a negative electrode by a Cat-CVD method on a current collector provided with a projection. [Comparative Example 2-3] A negative electrode active material layer containing Si and N was formed as a negative electrode by a Cat-CVD method on a current collector provided with a projection.夕3 [Comparative Example 2-4] A smooth copper foil (a foil of Rz.5/m, untreated foil) having no projections on both sides was formed, and a layer containing .Si and p active materials was formed by a Cat_CVD method. negative electrode. (Analysis of the composition of the negative electrode active material layer) The cross section of the negative electrode active material layer of the produced negative electrode was analyzed by linear fraction (4) (ΕΡΜΑ), and the ZAF repair component was quantified. The result is shown as 2 as a component concentration. Further, the subcomponent concentration indicates the ratio (mass%) of the subcomponent when the mass of the constituent elements of the entire layer is 嗖42/49 201236249 100. (Evaluation of Electrochemical Characteristics of Bismuth Electrode) The capacity retention rate at the 50th cycle was measured in the same manner as in Example 1. (矽 Weight measurement) For the negative electrode to be produced, the difference in weight of the current collector (including the protrusion) was obtained from the weight of the entire negative electrode as the weight of the crucible, and the result is shown in Table 3.

No. Collector surface protrusion 榘Electrical body Rz (μηι) Active material layer component Film thickness (Mm) Subcomponent concentration (mass%) Tannin t (mg) Initial release il; Capacity (mAh/g) 50th Hard Capacitance Credit (mAh/g) Capacity t Waiting Rate (%) Example 2-1 has 3 Si, Ρ 1 0.1 %P 0.004 3460 2510 73 Example 2-2 has 3 Si, P 1 Ι.5% 1) 0.019 3500 2850 81 贲Example 2-3 has 3 Si, Ρ 5 I.5%P 0.019 3570 2460 69 Implementation 洌2-4 There are 3 Si, Ρ, 0 5 I.5%P, 45%0 0.019 2820 2660 94 Implementation 2-5 with 3 Si, Ρ, 0 5 1.5%P, 0.7%O 0.019 3330 2580 77 Example 2-6 has 3 Si. Ρ, Ο 5 l.5%R 10%O 0.019 2930 2770 95 Example 2-7 with 3 Si, As 5 l%As 0.019 3365 2350 70 Example 2-8 with 3 Si, As, 0 5 l% As, 5% 0 0.019 2640 2420 92 Example 2-9 There are 0.9 Si, P 1.5% P 0.001 3315 1490 45 Comparative Example 2-1 There are 3 Si 5 — 0.019 3500 1750 50 Comparison 洌 2-2 There are 3 Si. B 0.1 % B 0.0041 3050 1355 44 Comparative Example 2-3 3 Si,N 1 0.1 %N 0.0039 2225 790 36 Comparative Example 2-4 1.5 Si, P (peeling) l.5% P (film-forming lowering) — — — - From the above results The negative electrode of the active material layer containing the second element (P, As) was used in Examples 2-1 to 2-8 as compared with the negative electrode having the active material layer composed only of Si in Comparative Example 2-1. The capacity retention rate after 50 cycles of discharge is greatly improved, wherein the atomic half of the second element 43/49 201236249 is approximately the atomic radius of S丨 (〇·Π7ηηι) and satisfies |(rA-r0)/r〇 |S〇.l relationship. Further, from the comparison between Example 2-2 and Example 2-9, it was confirmed that the negative electrode active material layer of the present invention significantly increases the discharge capacity by the combination of the current collector having a sufficiently large surface roughness Rz. And the capacity retention rate, and this is enough to further improve the charge and discharge cycle characteristics. Although the film thickness and the ruthenium mass of the negative electrode of Comparative Example 2 to Example 2-9 were small, only about half of the negative electrode had a discharge capacity and a capacity retention ratio which were not inferior to those of Comparative Example 2. Further, from the results of Examples 2-4, 2-6, and 2-8, it was confirmed that the active material was a layer aerobic, and the capacity retention ratio was higher, which was preferable. From the results of the examples, it was confirmed that a sufficient effect can be exhibited even when the oxygen content is 〇7 mass%. On the other hand, from the comparative examples 2-2 to 2-3, it was confirmed that the atomic half was introduced, and the element (Β, Ν) which did not satisfy the relationship of 丨(rA-丨.〇)/r〇S〇.l was confirmed. The valley maintenance rate of the negative electrode is greatly reduced. Further, from the results of Comparative Example 2_4, when the projections were not formed on the surface of the current collector, the current collector was not allowed to carry the negative electrode active material layer. In the present embodiment, P and As are used as the second element constituting the negative electrode active material layer, and oxygen is used as the third element. However, the negative electrode of the present invention is not limited thereto. As the second element, an element having a relationship in which at least the atomic radius satisfies |(rA-r〇)/r〇|$〇.l may be used, and it is presumed that, for example, Fe, Ni, and yttrium are used, except for p and 八3. , Co, Cu鲎, — Brother or 疋 use fluorine as the third element' can also achieve the same result. 44/49 In this embodiment, baking and capsule plating are performed as a method of roughening the current collector, but the method of forming the protrusion of the current collector of the present invention is not limited = 201236249 = as long as it can be on the surface of the current collector A method of forming a stable lion having a predetermined surface roughness is obtained, and the result of the same tendency as in the present embodiment is obtained by pushing (4). The above has described the present invention, but the present invention is limited to such an example. As long as it is the industry, the technical idea of the present invention is not available. Various modifications or corrections are conceivable, and it should be understood that ^ 4 of course also falls within the technical scope of the present invention. Illustratively, a schematic cross-sectional view of an example of a negative electrode for a nano battery for a secondary battery according to the first embodiment is shown. Fig. 2 is a view showing a manufacturing apparatus of nano-sized particles. FIG. 3 is a view showing a mixer used in the first embodiment of the first embodiment of the present invention. FIG. 4 is a view showing that the coating machine of the negative electrode according to the first embodiment is used to display the negative electrode for the secondary battery of the second embodiment. j ten section mode diagram. Fig. 6 is a cross-sectional view showing an example of the valve secondary battery of the present invention. [Main element symbol description] Negative electrode 3 Active material 4 Conductive material 5 Active material layer /: Adhesive material 7 Projection portion 45/49 201236249 9 Current collector 11 Lithium ion secondary battery 13 Positive electrode 15 Separator 17 Electrolyte 19 Battery can 21 Positive electrode lead 23 Negative electrode lead 25 Positive terminal 27 Sealing body 31 Nano-sized particle manufacturing device 33 Reaction chamber 35 Raw material powder supply port 37 Raw material Powder 39 Shielding gas supply port 41 Shielding gas 42 Carrier gas 43 MF coil 45 South frequency power source 47 Plasma 49 Filter 53 Mixer 55 Coating liquid 57 Coating liquid material 59 Coating machine 61 Negative electrode 46/49 201236249 63 65 67 Negative electrode activity Material layer protrusion negative electrode current collector 47/49

Claims (1)

201236249 VII. Patent application scope: 1. A negative electrode active material material for a lithium ion secondary battery, which is an active material material used for a negative electrode for a lithium ion secondary battery, characterized in that: Further, it is composed of particles of at least 5% by mass of element A, and the atomic radius Γα of the element A satisfies the relationship of l〇Vr0)/r〇|S〇.l with respect to the atomic radius rQ of the stone. 2. The negative electrode active material material for a lithium ion secondary battery according to claim 1, wherein the element A is selected from the group consisting of p, Cr, Mn, Fe, Co, Ni, Cu, and As. The element of the negative electrode active material for a lithium ion secondary battery according to claim 1, which further contains oxygen or fluorine. The negative electrode active material for a clock ion secondary battery according to the first aspect of the invention, wherein the average particle diameter of the particles of the primary particles is l〇nm~5/ζ m 〇 6. A negative electrode for a nonaqueous electrolyte secondary battery, comprising: an active = layer, the active material layer being on the surface or both sides of the negative electrode current collector, and coating the negative electrode activity of the "patent system" (4) The coating of the material and the grass 6 is formed. The negative electrode for the seed plasma secondary battery is characterized in that the anode active material having a negative electrode group and a thin crucible is n # , , , , The negative electrode active material layer is of the above-mentioned mass and is a main component and at least 70 atomic A is an atom of the atom A of the above-mentioned element A. 48/49 201236249 The diameter r〇 satisfies |(rA-r〇)/r The element of the relationship of 〇|S 0.] 7. The negative electrode for a lithium ion secondary battery according to claim 6, wherein the element A is selected from the group consisting of P, Cr, Mn, Fe, Co, Ni, Cu, The negative electrode for a lithium ion secondary battery according to the sixth aspect of the invention, wherein the negative electrode active material layer further contains oxygen or fluorine. Or a negative electrode for a lithium ion secondary battery of 6 or more, wherein the foregoing negative electrode current collecting system A foil is provided on the surface of the copper foil on which the surface of the active material layer is provided, and a surface portion Rz is set to have a surface roughness Rz of from 1/zm to 6 // m. In the negative electrode for a lithium ion secondary battery, the surface roughness Rz of the surface of the copper foil provided before the electrolytic graining treatment is 0.5 μm to 3 /zm. 11. A lithium ion II a secondary battery characterized by having a positive electrode, a negative electrode, and a separator, wherein the positive electrode is capable of occluding and discharging lithium ions; the negative electrode is a negative electrode according to claim 5 or 6; and the separator is And disposed between the positive electrode and the negative electrode; and the positive electrode, the negative electrode, and the separator are disposed in an electrolyte having lithium ion conductivity. 49/49