201110447 六、發明說明 【發明所屬之技術領域】 本發明爲有關一種使用於鋰離子蓄電池的鋰離子蓄電 池用負極材料，及其製造方法，與使用該鋰離子蓄電池用 負極材料的鋰離子蓄電池。 【先前技術】 近年來’由於攜帶機器的小型化及高性能化，對其所 搭載的蓄電池的能量密度的要求越來越高。其中，鋰離子 蓄電池與鎳鎘蓄電池或鎳氫蓄電池相比，顯示更高的電 壓、更更高充放電容量（能量密度），因此，開始被廣泛地 使用爲上述攜帶機器的電源》 鋰離子蓄電池主要由負極材料、正極材料、將該些電 極材料絕緣的隔離材料、輔助電極材料間的電荷移動的電 解液、放置該些的電池盒所構成。而且，鋰離子蓄電池用 負極材料’爲於集電材料的銅箔或銅合金箔上塗敷負極活 性物質的材料所構成，負極活性物質，通常爲使用石墨系 碳材料。但是，因石墨系碳材料的放電容量已達到理論容 量（3 7 2mAh/g)，所以需尋求具有更高的放電容量及充電容 S之負極活性物質。 因此’開始對可顯示更高充放電容量的負極活性物質 之Si、Ge' Ag、In、Sn及Pb等，可以與鋰合金化的金屬 進行硏究。例如在專利文獻1提出一種將約爲石墨系碳材 料的2.5倍的993mAh/g的理論充放電容量的Sn蒸鍍在集 201110447 電體表面所得時的負極材料。但是，因Sn在鋰離子的充 放電時（與鋰的合金化、鋰之釋出），於重複進行體積膨脹 與收縮’由此’ Sn會由集電體剝離而造成電阻增大，或 S η自身破裂而導致s η之間的接觸電阻增大.，因此，結果 仍存在著充放電容量大幅降低的問題。 解決該問題的方法，一般爲緩和負極活性物質的體積 變化’例如在專利文獻2中提出一種將S η等金屬奈米結 晶的表面進行碳塗敷的金屬奈米結晶複合體，或將金屬奈 米結晶複合體用碳塗敷層連結的金屬奈米結晶複合體，與 聚偏氟乙烯（PVDF)等結合材料與石墨混合，並塗佈在銅 集電體上後，進行真空燒結而成的負極材料。 專利文獻1 :日本特開2 0 0 2 - 1 1 0 1 5 1號公報 專利文獻2 :日本特開2007-305569號公報 【發明內容】 但是，在目前的技術中，仍存在如下所示的問題。 在專利文獻2的負極材料中，因吸留鋰的金屬結晶爲 奈米尺寸’所以吸留鋰所引起的體積變化較小，且可提高 充放電容量，但爲了使用結合材料進行金屬奈米結晶複合 體之間的結合，即使添加了石墨，負極電極材料的導電性 也會變差。因此’在需要如汽車般進行高速充放電的用途 中’仍存在不能經由大電流，造成充放電容量降低的問 題。 本發明是鑒於上述課題而完成的發明，而以提供一種 _ 6 - 201110447 具有高充放電容量，且可以改善伴隨充放電循環所造成的 負極活性物質的劣化，並且可以以高速充放電的鋰離子蓄 電池用負極材料’及其製造方法，與使用鋰離子蓄電池用 負極材料的鋰離子蓄電池。 解決上述課題的方法，本發明之鋰離子蓄電池用負極 材料，爲使用於鋰離子蓄電池之鋰離子蓄電池用負極材 料’其特徵爲’前述鋰離子蓄電池用負極材料是在負極集 電體上形成負極活性物質而成的，前述負極活性物質是在 非晶質碳中分散l〜40at%的Sn與3〜20at%的選自4A、 5A、6A族元素中的至少一種以上的金屬（以下亦稱爲 4A、5A、6A族元素）而成。 依據此種構成，Sn不與碳進行合金化而以奈米粒子 尺寸分散在非晶質碳中，另一方面，4A、5A、6A族元素 與碳結合，以奈米粒子尺寸的碳化物分散在非晶質碳中。 而且，S η經由非晶質碳的結晶構造中的sp 3結合抑製吸留 鋰引起的體積膨脹。因此，在提高充放電容量（相對質量 容量或相對體積容量）的同時，亦可提高循環特性（即使 重複充放電的循環，負極活性物質也不會劣化（剝離、脫 落等）之充放電容量不會降低的性質）。另一方面，因分 散在非晶質碳中的4A、5A、6A族元素的碳化物具有高導 電性，因此，可提高膜的導電性。因此，即使在大電流中 電子也容易流動，而可高速充放電。 本發明之鋰離子蓄電池用負極材料的製造方法爲，請 求項1記載之鋰離子蓄電池用負極材料的製造方法，其特 201110447 徵爲’經由氣相沈積法，在負極集電體上形成1〜40 at%的 Sn與3〜20at%的選自4A、5 A、6A族元素中的至少一種以 上的金屬分散於非晶質碳中而成的負極活性物質。 依據此種製造方法，使用氣相沈積法，可有效地使 Sn分散於非晶質碳中的同時，使4A、5A、6A族元素以 碳化物方式分散在非晶質碳中。又，可使非晶質碳，及規 定的金屬組成的控制，或負極活性物質對被膜厚度的控制 變得更容易，可以使負極集電體上的負極活性物質的形成 更爲容易且簡便地進行。 又，本發明的鋰離子蓄電池用負極材料的製造方法， 其特徵爲，前述負極活性物質的非晶質碳之形成爲使用石 墨標靶，經由電弧離子鍍法進行。 依據此種製造方法，可以加速成膜速度，而實現厚膜 化，又，經由形成多石墨構造的膜，而容易吸留鋰。 本發明的鋰離子蓄電池，其特徵爲，使用請求項1的 鋰離子蓄電池用負極材料。 依據此種構成，經由使用本發明的鋰離子蓄電池用負 極材料時，可以形成具有更高充放電容量，優良循環特 性，且可高速充放電的鋰離子蓄電池。 依據本發明的鋰離子蓄電池用負極材料，因具有高充 放電容量，且可改善伴隨充放電循環所造成的負極活性物 質劣化的性質，從而可以製造具有優良循環特性的鋰離子 蓄電池。而且，經由導電性提高，也可高速充放電。 依據本發明的鋰離子蓄電池用負極材料的製造方法， -8- 201110447 在負極活性物質中，可以將1〜40at%的Sn與3〜20at%的 選自4A、5 A、6A族元素中的至少一種以上的金屬有效分 散於非晶質碳中。又，可以容易地進行非晶質碳，及該些 金屬的組成的控制，或負極活性物質的被膜厚度的控制， 可以使負極活性物質容易且簡便地形成在負極集電體上。 又，經由使用石墨標靶的電弧離子鍍法，可以實現厚 膜化，並且可以形成容易吸留鋰的膜。 本發明的鋰離子蓄電池具有更高充放電容量，具有優 良循環特性，且可高速充放電。 以下，將參照附圖對本發明的鋰離子蓄電池用負極材 料，及其製造方法，與鋰離子蓄電池進行詳細說明。 《鋰離子蓄電池用負極材料》 如圖1所示，本發明的鋰離子蓄電池用負極材料（以 下亦稱爲負極材料）1〇，具有負極集電體1、形成在負極 集電體1上的負極活性物質2，負極活性物質2是 1〜40at%的 Sn作爲金屬奈米粒子、3〜20at%的選自4A、 5A、6A族元素中的至少一種以上的金屬（以下亦稱爲 4A、5A、6A族元素）作爲碳化物奈米粒子而分散在非晶質 碳中所得的物質。 以下’，將對各構成進行說明。 <負極集電體> 負極集電體1的材質需要具有可耐受負極活性物質2 -9- 201110447 膨脹的應力的機械特性。在拉伸較大（容易塑性變形、耐 力小）的材質中，伴隨負極活性物質2的膨脹，會產生拉 伸（塑性變形）’或發生褶皺或彎折等。由該些理由得知， 負極集電體1的材質’一般爲使用銅、銅合金、鎳、不銹 鋼等金屬’其中’就容易對薄膜加工與成本之觀點而言， 以耐力大、斷裂拉伸爲2%左右以下之銅箔或銅合金箔爲 佳。又，抗拉強度越高則越良好，以至少700N/mm2以上 的抗拉強度爲佳。就此點而言，相對於電解銅箔以使用壓 延銅合金箔爲更佳。此種高強度的銅合金箔，例如可列舉 使用含有Ni或Si的所謂的科森系銅合金的箔。 負極集電體1的厚度較佳爲1〜50//m。在厚度不足1 /zm時’負極集電體1不能耐受在負極集電體1表面形成 負極活性物質2時的應力’可能在負極集電體1上產生斷 裂或龜裂。另一方面，在厚度超過50;zm時，製造成本 增加，又’電池可能大型化。又，更較佳爲的爲5~2〇 β m。 <負極活性物質> [非晶質碳] 非晶質碳具有碳的S p 2與s p 3結合’例如顯示類金剛 石碳那樣的結晶構造。上述構造中的碳的S p3結合起到抑 製充放電時的分散於非晶質碳中的金屬的體積變化的作 用。又’從充放電容量增大這點來說，非晶質碳較佳爲具 有吸留石墨構造等的鋰的構造。 -10- 201110447 [Sn及選自4A、5A、6A族元素中的至少一種以上的 金屬] 811的組成爲1~40&1%，選自4八'5八、6八族元素中的 至少一種以上的金屬的組成爲3〜20at% ^ 因Sn爲可以與鋰合金化的同時熔點低的金屬，所以 與熔點高的碳非合金化而分散於非晶質碳中。又，4A、 5A、6A族元素是與Sn製作金屬間化合物的金屬，在存在 碳的情形下，大部分不與Sn結合而與碳結合形成碳化 物，分散於非晶質碳中。因此，形成爲在非晶質碳中分散 Sn的金屬奈米粒子、4A、5A、6A族元素的碳化物的奈米 粒子的構造。 經由將1〜40at%的Sn分散在非晶質碳中（分散爲奈米 晶簇狀），與在負極集電體上塗佈石墨而成的負極材料相 比，可以形成優良之充放電容量（相對質量容量或相對體 積容量），且循環特性不會劣化的負極材料1 0。又，增加 相對質量容量的金屬，有Si及Sn，增加相對體積容量的 金屬，有 Si、Ag、In、Sn 及 Bi。 另一方面，經由將4A、5A、6A族元素（即4A、5A、 6A族元素的碳化物）分散在非晶質碳中（分散爲奈米晶簇 狀），可提高導電性（電子導電性）。即，因該些碳化物具 有高導電性，所以可以形成電子的導電路徑而高速充放 電。 負極活性物質2中的Sn含量爲1 ~40at%。經由添加 Sn，可以實現提高充放電容量及循環特性，特別是經由將 201110447 含量設定在該範圍內，可進一步增大充放電容量，又，即 使反復進行充放電後，因可以經由碳矩陣緩和Sn的體積 變化，所以可以得到良好的循環特性。在Sn含量不足 1 at%時，增大充放電容量的效果較少。又，爲了進一步提 高充放電容量，較佳爲5at%以上，更較佳爲l〇at%以上。 另一方面，Sn的含量超過40 at%時，不能經由碳矩陣緩和 Sn的體積變化，雖然初期充放電容量高，但膜構造破壞 而循環特性大幅降低。又，爲了進一步提高循環特性，較 佳爲35at%以下，更較佳爲30at%以下。 4A、5A、6A族元素的含量爲3〜20at%。 4A、5A、6A族元素的含量不足3at%時，因不能提高 導電性，故不能高速充放電。另一方面，超過20at%時， 因碳化物的比例增加，而使負極活性物質中的鋰原子的擴 散受到抑製，因此，不能高速充放電。 在此，分散於非晶質碳中的 Sn的粒徑較佳爲 0.5〜lOOnm。經由粒徑分散爲〇. 5 ~ 1 0 0 nm的奈米晶簇狀， 可以進一步使充放電時的金屬的體積變化更爲緩和。又， 4A、5A、6A族元素的碳化物的粒徑較佳爲2〜30nm »如 果粒徑爲2nm以上，則可容易提高導電性，如果爲3〇nm 以下則難以阻礙鋰的擴散。 此種Sn或4A、5A、6A族元素的碳化物的粒徑的控 制，可以經由控制負極活性物質2中的碳和該些金屬的組 成方式進行。又，組成的控制可以經由在負極集電體1上 形成負極活性物質2時的成膜條件進行控制。又，此種 -12- 201110447[Technical Field] The present invention relates to a negative electrode material for a lithium ion secondary battery used in a lithium ion secondary battery, a method for producing the same, and a lithium ion secondary battery using the negative electrode material for a lithium ion secondary battery. [Prior Art] In recent years, due to the miniaturization and high performance of portable devices, the energy density of the batteries to be mounted has become higher and higher. Among them, a lithium ion battery exhibits a higher voltage and a higher charge and discharge capacity (energy density) than a nickel-cadmium battery or a nickel-hydrogen battery, and therefore, it is widely used as a power source for the above-mentioned portable device. It is mainly composed of a negative electrode material, a positive electrode material, an insulating material that insulates the electrode materials, an electrolyte that moves electric charges between the auxiliary electrode materials, and a battery case in which these are placed. Further, the negative electrode material for lithium ion secondary batteries is composed of a material for coating a negative electrode active material on a copper foil or a copper alloy foil of a current collector, and a negative electrode active material is usually a graphite-based carbon material. However, since the discharge capacity of the graphite-based carbon material has reached the theoretical capacity (37 2 mAh/g), it is necessary to find a negative electrode active material having a higher discharge capacity and a charge capacity S. Therefore, Si, Ge'Ag, In, Sn, and Pb, which can exhibit a higher charge and discharge capacity of the negative electrode active material, can be studied with lithium alloyed metal. For example, Patent Document 1 proposes a negative electrode material obtained by vapor-depositing Sn having a theoretical charge/discharge capacity of about 993 mAh/g of about 2.5 times that of a graphite-based carbon material on the surface of the electric body of 201110447. However, when Sn is charged and discharged by lithium ions (alloying with lithium and releasing lithium), volume expansion and contraction are repeated, and thus Sn is peeled off from the current collector to cause an increase in electric resistance, or S. The η itself ruptures and the contact resistance between s η increases. Therefore, there is still a problem that the charge and discharge capacity is largely lowered. A method for solving this problem is generally to alleviate the volume change of the negative electrode active material. For example, Patent Document 2 proposes a metal nanocrystal composite in which a surface of a metal nanocrystal such as S η is carbon-coated, or a metal naphthalene. A metal nanocrystal composite in which a rice crystal composite is bonded by a carbon coating layer, and a bonding material such as polyvinylidene fluoride (PVDF) is mixed with graphite, coated on a copper current collector, and then vacuum sintered. Anode material. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. 2007-305569. SUMMARY OF THE INVENTION However, in the prior art, there are still the following problem. In the negative electrode material of Patent Document 2, since the metal crystal which occludes lithium has a nanometer size, the volume change caused by occluding lithium is small, and the charge and discharge capacity can be improved, but in order to use the bonding material for metal nanocrystallization The bonding between the composites, even if graphite is added, the conductivity of the negative electrode material is deteriorated. Therefore, in the case where it is required to perform high-speed charge and discharge as in a car, there is still a problem that a large current cannot be passed, resulting in a decrease in charge and discharge capacity. The present invention has been made in view of the above problems, and provides a lithium ion having a high charge and discharge capacity, which can improve deterioration of a negative electrode active material caused by a charge and discharge cycle, and can be charged and discharged at a high speed. A negative electrode material for a battery and a method for producing the same, and a lithium ion secondary battery using a negative electrode material for a lithium ion secondary battery. In the method for solving the above problems, the negative electrode material for a lithium ion secondary battery of the present invention is a negative electrode material for a lithium ion secondary battery used in a lithium ion secondary battery, characterized in that the negative electrode material for a lithium ion secondary battery is a negative electrode formed on a negative electrode current collector. The negative electrode active material is one in which at least one of 4A, 5A, and 6A elements selected from the group consisting of Sn and 3 to 20 at% of Sn in amorphous carbon is dispersed in amorphous carbon (hereinafter also referred to as It is made up of 4A, 5A, and 6A elements. According to this configuration, Sn is not alloyed with carbon and dispersed in amorphous carbon in a nanoparticle size. On the other hand, elements of Groups 4A, 5A, and 6A are combined with carbon to disperse carbides in a nanoparticle size. In amorphous carbon. Further, S η suppresses volume expansion caused by occlusion of lithium via sp 3 bonding in the crystal structure of amorphous carbon. Therefore, the charge/discharge capacity (relative mass capacity or relative volume capacity) can be increased, and the cycle characteristics can be improved (the charge/discharge capacity of the negative electrode active material does not deteriorate (peeling, falling off, etc.) even if the cycle of charge and discharge is repeated. Will reduce the nature). On the other hand, since the carbides of the 4A, 5A, and 6A elements dispersed in the amorphous carbon have high conductivity, the conductivity of the film can be improved. Therefore, even in a large current, electrons easily flow, and can be charged and discharged at a high speed. The method for producing a negative electrode material for a lithium ion secondary battery according to the present invention is the method for producing a negative electrode material for a lithium ion secondary battery according to claim 1, wherein the method of forming a negative electrode current collector is formed by a vapor deposition method. 40 at% of Sn and 3 to 20 at% of a negative electrode active material obtained by dispersing at least one or more metals selected from the group consisting of 4A, 5 A, and 6A elements in amorphous carbon. According to this production method, the vapor deposition method can effectively disperse Sn in the amorphous carbon and disperse the 4A, 5A, and 6A elements in the amorphous carbon as a carbide. Further, it is possible to control the amorphous carbon and the predetermined metal composition, or to control the thickness of the negative electrode active material, and to facilitate the formation of the negative electrode active material on the negative electrode current collector. get on. Further, in the method for producing a negative electrode material for a lithium ion secondary battery of the present invention, the formation of amorphous carbon of the negative electrode active material is carried out by using an arc ion plating method using a graphite target. According to this production method, it is possible to accelerate the film formation speed to achieve thick film formation, and it is easy to store lithium through the formation of a film having a multi-graphite structure. A lithium ion secondary battery of the present invention is characterized by using the negative electrode material for a lithium ion secondary battery of claim 1. According to this configuration, when the negative electrode material for a lithium ion secondary battery of the present invention is used, a lithium ion secondary battery having a higher charge and discharge capacity, excellent cycle characteristics, and high-speed charge and discharge can be formed. According to the negative electrode material for a lithium ion secondary battery of the present invention, since it has a high charge and discharge capacity and can improve the deterioration of the negative electrode active material accompanying the charge and discharge cycle, a lithium ion secondary battery having excellent cycle characteristics can be produced. Further, it is also possible to charge and discharge at a high speed by improving conductivity. According to the method for producing a negative electrode material for a lithium ion secondary battery of the present invention, -8 to 201110447, in the negative electrode active material, 1 to 40 at% of Sn and 3 to 20 at% of elements selected from the group consisting of 4A, 5 A, and 6A elements may be used. At least one or more metals are effectively dispersed in the amorphous carbon. Further, the amorphous carbon, the control of the composition of the metals, or the control of the thickness of the negative electrode active material can be easily controlled, and the negative electrode active material can be easily and easily formed on the negative electrode current collector. Further, by the arc ion plating method using a graphite target, thick film formation can be achieved, and a film which easily occludes lithium can be formed. The lithium ion secondary battery of the present invention has a higher charge and discharge capacity, has excellent cycle characteristics, and can be charged and discharged at a high speed. Hereinafter, a negative electrode material for a lithium ion secondary battery of the present invention, a method for producing the same, and a lithium ion secondary battery will be described in detail with reference to the accompanying drawings. "Negative Electrode Material for Lithium Ion Batteries" As shown in FIG. 1, the negative electrode material for lithium ion battery (hereinafter also referred to as negative electrode material) of the present invention has a negative electrode current collector 1 and is formed on the negative electrode current collector 1. In the negative electrode active material 2, the negative electrode active material 2 is 1 to 40 at% of Sn as metal nanoparticles, and 3 to 20 at% of at least one metal selected from the group consisting of 4A, 5A, and 6A elements (hereinafter also referred to as 4A, The 5A, 6A element) is a substance obtained by dispersing in amorphous carbon as a carbide nanoparticle. Hereinafter, each configuration will be described. <Negative Current Collector> The material of the negative electrode current collector 1 is required to have mechanical characteristics capable of withstanding the stress of the negative electrode active material 2 -9-201110447 expansion. In the material having a large tensile force (easily plastically deformed and low in endurance), stretching (plastic deformation) or wrinkles or bending may occur depending on the expansion of the negative electrode active material 2. For these reasons, the material of the negative electrode current collector 1 is generally a metal such as copper, copper alloy, nickel or stainless steel, which is easy to handle and cost. It is preferably a copper foil or a copper alloy foil of about 2% or less. Further, the higher the tensile strength, the better the tensile strength is at least 700 N/mm2 or more. In this regard, it is more preferable to use a rolled copper alloy foil with respect to the electrolytic copper foil. As such a high-strength copper alloy foil, for example, a foil of a so-called Corson-based copper alloy containing Ni or Si is used. The thickness of the anode current collector 1 is preferably from 1 to 50/m. When the thickness of the negative electrode current collector 1 is not able to withstand the formation of the negative electrode active material 2 on the surface of the negative electrode current collector 1 when the thickness is less than 1 / zm, it may cause cracking or cracking on the negative electrode current collector 1. On the other hand, when the thickness exceeds 50; zm, the manufacturing cost increases, and the battery may be enlarged. Further, it is more preferably 5 to 2 〇 β m. <Negative Electrode Active Material> [Amorphous Carbon] The amorphous carbon has a combination of S p 2 and s p 3 of carbon', for example, a crystal structure such as a diamond-like carbon. The Sp3 bonding of carbon in the above structure serves to suppress the volume change of the metal dispersed in the amorphous carbon at the time of charge and discharge. Further, the amorphous carbon is preferably a structure having lithium such as a absorbing graphite structure, from the viewpoint of an increase in charge and discharge capacity. -10- 201110447 [Sn and at least one metal selected from the group consisting of 4A, 5A, and 6A elements] 811 has a composition of 1 to 40 & 1%, and is at least selected from the group consisting of 4, 8 '5, and 6 8 elements. The composition of one or more kinds of metals is 3 to 20 at%. Since Sn is a metal which can be alloyed with lithium and has a low melting point, it is not alloyed with carbon having a high melting point and is dispersed in amorphous carbon. Further, the 4A, 5A, and 6A elements are metals which form an intermetallic compound with Sn. When carbon is present, most of them do not combine with Sn and combine with carbon to form a carbide, which is dispersed in amorphous carbon. Therefore, the structure of the nanoparticle of the metal nanoparticle of Sn and the carbide of the 4A, 5A, and 6A elements in the amorphous carbon is formed. By dispersing 1 to 40 at% of Sn in amorphous carbon (dispersed in a nanocrystalline cluster shape), it is possible to form an excellent charge and discharge capacity as compared with a negative electrode material obtained by coating graphite on a negative electrode current collector. The negative electrode material 10 (relative mass capacity or relative volume capacity) and which does not deteriorate in cycle characteristics. Further, a metal having a relatively high mass capacity, Si and Sn, and a metal having a relatively large volume capacity are Si, Ag, In, Sn, and Bi. On the other hand, by dispersing 4A, 5A, and 6A elements (i.e., carbides of Group 4A, 5A, and 6A elements) in amorphous carbon (dispersed into a nanocrystalline cluster), conductivity can be improved (electron conduction) Sex). That is, since these carbides have high conductivity, it is possible to form an electron conductive path and charge and discharge at a high speed. The Sn content in the negative electrode active material 2 is 1 to 40 at%. By adding Sn, it is possible to improve the charge/discharge capacity and cycle characteristics. In particular, by setting the 201110447 content within this range, the charge/discharge capacity can be further increased, and even after repeated charge and discharge, Sn can be alleviated via the carbon matrix. The volume changes so that good cycle characteristics can be obtained. When the Sn content is less than 1 at%, the effect of increasing the charge and discharge capacity is less. Further, in order to further increase the charge and discharge capacity, it is preferably 5 at% or more, and more preferably 10 at% or more. On the other hand, when the content of Sn exceeds 40 at%, the volume change of Sn cannot be alleviated by the carbon matrix, and although the initial charge and discharge capacity is high, the film structure is broken and the cycle characteristics are largely lowered. Further, in order to further improve the cycle characteristics, it is preferably 35 at% or less, more preferably 30 at% or less. The content of the 4A, 5A, and 6A elements is 3 to 20 at%. When the content of the 4A, 5A, and 6A elements is less than 3 at%, the conductivity cannot be improved, so that the charge and discharge cannot be performed at a high speed. On the other hand, when it exceeds 20 at%, the proportion of the carbide increases, and the diffusion of lithium atoms in the negative electrode active material is suppressed, so that the charge and discharge cannot be performed at a high speed. Here, the particle diameter of Sn dispersed in the amorphous carbon is preferably 0.5 to 100 nm. The volume distribution of the metal at the time of charge and discharge can be further moderated by the nanocrystal cluster shape in which the particle diameter is dispersed to 〇5 to 100 nm. Further, the particle diameter of the carbide of the 4A, 5A, and 6A elements is preferably 2 to 30 nm. » If the particle diameter is 2 nm or more, the conductivity can be easily improved, and if it is 3 Å or less, it is difficult to inhibit the diffusion of lithium. The control of the particle size of the carbide of such Sn or 4A, 5A, and 6A elements can be carried out by controlling the carbon in the negative electrode active material 2 and the composition of the metals. Further, the control of the composition can be controlled by the film formation conditions when the anode active material 2 is formed on the anode current collector 1. Again, this -12- 201110447
Sn或4A、5A、6A族元素的碳化物的粒徑的測定，可以 經由以用FIB-TEM觀察或薄膜X(愛克斯）射線衍射觀 察的金屬的衍射線強度的半輻値爲基礎進行。而且，該些 金屬組成的分析可以經由奧杰（Auger )電子質譜分析 (AES分析）進行。 《鋰離子蓄電池用負極材料的製造方法》 本發明的鋰離子蓄電池用負極材料10的製造方法 爲，將1〜40at%的Sn、與3〜20at%的選自4A、5A、6A族 元素中的至少一種以上的金屬（金屬的碳化物）分散於非晶 質碳中而成的負極活性物質2，經由氣相沈積法形成在負 極集電體1上。 負極材料10的製造方法包含負極集電體形成步驟與 負極活性物質形成步驟，其經由負極集電體形成步驟形成 負極集電體1後，經由負極活性物質形成步驟，將 1〜40at%的Sn、與3~20at%的選自4A、5A、6A族元素中 的至少一種以上的金屬的碳化物分散於非晶質碳中而成的 負極活性物質2，經由氣相沈積法形成在該負極集電體1 上。 以下’對各步驟進行說明。 <負極集電體形成步驟> 負極集電體形成步驟爲形成負極集電體1的步驟。 即’是爲了形成負極活性物質2而準備負極集電體1的步 -13- 201110447 驟。負極集電體1，如上前述，只要使用公知的負極集電 體1即可。又’經由負極集電體形成步驟，可以實施負極 集電體1的變形的校正或硏磨等。 <負極活性物質形成步驟> 負極活性物質形成步驟爲將l〜4〇at%的Sn、與 3〜20at°/〇的選自4A、5A、6A族元素中的至少—種以上的 金屬的碳化物，經由氣相沈積法分散於非晶質碳中，同 時，經由向上述非晶質碳中的Sn或碳化物的分散形成的 負極活性物質2，形成在負極集電體1上的步驟。 經由使用氣相沈積法，將卜4〇at%的Sn、與3~20at% 的選自4A、5A、6A族元素中的至少一種以上的金屬的碳 化物，以奈米晶簇狀分散於非晶質碳中，同時，可以在負 極集電體1上形成負極活性物質2。又，可以將非晶質 碳，以及Sn或4A、5A、6A族元素的組成自由控制在寬 的範圍內，同時，也可以容易地控制被膜厚度，可以使負 極活性物質2容易且簡便地形成在負極集電體1上。 又，在本發明的製造方法中，因爲使用氣相沈積法， 因此，使將Sn或4A、5A、6A族元素的碳化物分散在非 晶質碳中而成的膜經由蒸鍍形成在負極集電體1上而得到 負極材料1 〇。因此，可以省略目前的製造方法中的、將 石墨質碳粉末塗佈在負極集電體上的步驟、使塗佈的粉末 乾燥的步驟，及將塗佈並乾燥的粉末按壓在負極集電體而 提高密度的步驟。 -14- 201110447 氣相沈積法，可以使用化學氣相沈積法（CVD : Chemical Vapor Deposition 法）或物理氣相沈積法 (PVD : Physical Vapor Deposition 法）等，CVD 法有等 離子CVD法，PVD法有真空蒸鍍法、濺射法、離子鍍 法、電弧離子鍍法（AIP ) '鐳射消融法等。特別是需要 厚膜化時，需要使用成膜速度快的方法，對此，以AIP法 爲有效。例如，如果將靶材作爲石墨而進行電弧放電，則 石墨經由電弧放電的熱而形成碳原子或離子蒸發，可以在 負極集電體表面堆積非晶質碳。進而，在使用石墨標祀的 A IP法中’因除電弧放電產生的來自靶材表面的碳原子或 離子以外’從數；zm到數十；t/m的石墨的微粒子（宏觀粒 子）也會飛出並在負極集電體上堆積，因此，與濺射法或 離子鍍法相比，可以形成石墨構造多的膜。因此，可以形 成進一步吸留鋰的膜。在經由該AIP法形成非晶質碳膜的 同時’在同一腔室內，如果將Sn及4A、5A、6A族元素 經由真空蒸鍍法或濺射法進行蒸發，則可以形成含有Sn 及4A、5A、6A族元素的碳化物的非晶質碳膜（負極活性 物質）。又，在經由AIP法進行放電時，邊導入甲烷或乙 烯等烴氣體邊實施時，經由電弧放電，該些烴氣體分解並 以非晶質碳膜堆積在負極集電體表面，因此，可以進一步 提局成膜速度。 隨後，參照圖2、3 ’對使用濺射法的情形及使用a IP 法的情形的鋰離子蓄電池用負極材料1 〇的製造方法的— 例進行說明，只要是使用氣相沈積法的材料，則不限定於 -15- 201110447 該些材料。又，在此，對使用Sn(錫）與Zr(锆）的情形進行 說明。又，濺射裝置及AIP-濺射複合裝置的構成不限定 於用圖2、3所示的構成，可以使用公知的裝置。 對於使用濺射法的情形，如圖2所示，首先在濺射裝 匱20的腔室21內設置φ lOOmmx厚度5mm的碳靶22、錫 靶23，及锆靶24，並將長5 Ox寬50x厚度0.02 mm的銅箔 25依對向於碳靶22、錫靶23，及锆靶24的方式設置在 基板台26。隨後，依腔室21內的壓力爲lx l(T3Pa以下的 方式抽真空，使腔室21內處於真空狀態。其後，在腔室 21內導入Ar氣體，使腔室21內的壓力變爲0.26Pa，對 碳靶22、錫靶23，及鍩靶24施加DC(直流）而產生等離 子，濺射碳靶22、錫靶23，及鍩靶24。由此，在銅箔25 上成膜在非晶質碳中分散有錫及銷碳化物的膜（負極活性 物質）。由此，可以製造鋰離子蓄電池用負極材料。 對於使用AIP法的情形，如圖3所示，首先在AIP-濺射複合裝置30的腔室31內，設置φ 10Ommx厚度16mm 的石墨標靶32，及φ6英寸X厚度6mm的錫靶33與錯靶 34，並將長50χ寬50x厚度0.02mm的銅箔35設置在公轉 的圓筒狀的基板台36表面。隨後，依腔室31內的壓力爲 lxl(T3Pa以下的方式抽真空，使腔室31內處於真空狀 態。其後’在腔室3 1內導入Ar氣體，使腔室3 1內的壓 力變爲0.26Pa，對石墨標靶32、錫靶33，及锆靶34施加 DC(直流），從而使石墨標靶32產生電弧放電，使錫靶33 及鲒靶34產生輝光放電，使石墨經由電弧放電的熱進行 -16- 201110447 蒸發，並且使錫及锆經由氬的濺射進行蒸發。由此，在銅 箔35上成膜在非晶質碳中分散有錫及鉻碳化物的膜（負極 活性物質）。如此，即可製造鋰離子蓄電池用負極材料。 又，每次進行本發明時，在不對上述各步驟產生不良 影響的範圍內，在上述各步驟之間或前後可以包含例如負 極集電體清洗步驟、溫度調整步驟等，也可包含其他步 驟。 《鋰離子蓄電池》 本發明的鋰離子蓄電池爲使用上述記載的鋰離子蓄電 池用負極材料的電池。經由使用本發明的負極材料，可以 製造具有更高充放電容量，優良循環特性且可高速充放電 的鋰離子蓄電池。 《鋰離子蓄電池的形態》 鋰離子蓄電池的形態，可以舉出圓筒型、硬幣型、基 板搭載薄膜型、角型、薄片型等，只要可以使用本發明的 負極材料，則可以爲各種方式。 鋰離子蓄電池主要由負極材料、正極材料、將該些電 極材料絕緣的隔離材料、輔助電極材料間的電荷移動的電 解液、放置該些的電池盒所構成。 以下’對各構成進行說明。 <負極材料 -17- 201110447 負極材料使用上述的本發明的負極材料，又，該負極 材料經由上述發明的製造方法進行製造。 <正極材料> IE極材料沒有特別的限定，可以使用公知的材料例如 LiC〇02、LiNi〇2、LiMn204等含鋰氧化物。對正極材料的 製造方法也沒有特別限定，可以利用公知的方法，例如對 &末狀的該些正極材料添加膠黏劑並依據需要添加導電材 料 '溶劑等並進行充分混煉後，塗佈在鋁箔等集電體上， 並進行乾燥、擠壓而進行製造。 <隔離材料> 隔離材料沒有特別限定，可以使用公知的材料，例如 聚乙嫌 ' 聚丙烯等聚烯烴爲原料的多孔質體的片材或不織 布等的隔離材料。 <電解液> 電解液注入電池盒內並進行密閉。該電解液在充放電 時’可以進行因在負極材料及正極材料上的電化學反應而 使生成的鋰離子移動。 電解液的電解質用溶劑，可以使用可溶解鋰鹽的公知 的非質子性、低介電常數的溶劑。例如，可以單獨或混合 多個以下溶劑使用，前述溶劑爲：碳酸亞乙酯、碳酸亞丙 酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、乙睛、丙 -18- 201110447 腈、四氫呋喃、r-丁內酯、2-甲基四氫呋喃、丨，3_二氧雜 戊環、4_甲基- I，3-二氧雜戊環、丨，2-二甲氧基乙烷、丨，2_ 二乙氧基乙烷、二乙基醚、環丁颯、甲基環丁颯、硝基甲 院、N，N-二甲基甲醯胺、二甲基亞颯等溶劑。 電解液的電解質使用的鋰鹽，可以使用例如The measurement of the particle diameter of the carbide of Sn or the group 4A, 5A, and 6A elements can be carried out based on the half-twist of the diffraction line intensity of the metal observed by FIB-TEM observation or film X (Aix) ray diffraction. Moreover, the analysis of these metal compositions can be carried out by Auger electron mass spectrometry (AES analysis). <<Method for Producing Anode Material for Lithium Ion Batteries>> The method for producing a negative electrode material 10 for a lithium ion battery according to the present invention is to use 1 to 40 at% of Sn and 3 to 20 at% of elements selected from 4A, 5A, and 6A elements. The negative electrode active material 2 in which at least one or more metals (metal carbides) are dispersed in amorphous carbon is formed on the negative electrode current collector 1 by a vapor deposition method. The method for producing the negative electrode material 10 includes a negative electrode current collector forming step and a negative electrode active material forming step, and after the negative electrode current collector 1 is formed via the negative electrode current collector forming step, 1 to 40 at% of Sn is passed through the negative electrode active material forming step. The negative electrode active material 2 obtained by dispersing 3 to 20 at% of a carbide of at least one metal selected from the group consisting of 4A, 5A, and 6A elements in amorphous carbon is formed on the negative electrode via a vapor deposition method. Collector 1 is on. The following steps will be described. <Negative Current Collector Forming Step> The negative electrode current collector forming step is a step of forming the negative electrode current collector 1. That is, the step of preparing the negative electrode current collector 1 for forming the negative electrode active material 2 is -13-201110447. As described above, the negative electrode current collector 1 may be any known negative electrode current collector 1. Further, the correction of the deformation of the negative electrode current collector 1 or the honing or the like can be performed via the negative electrode current collector forming step. <Negative Electrode Active Material Forming Step> The negative electrode active material forming step is a metal having at least one or more selected from the group consisting of 4 to 4 at% of Sn and 3 to 20 at °/〇 selected from 4A, 5A, and 6A elements. The carbide is dispersed in the amorphous carbon by a vapor deposition method, and is formed on the anode current collector 1 via the anode active material 2 formed by dispersing Sn or carbide in the amorphous carbon. step. By using a vapor deposition method, a carbide of at least one of 3 to 20 at% of a metal selected from the group consisting of 4A, 5A, and 6A elements is dispersed in a nanocrystalline cluster. In the amorphous carbon, at the same time, the anode active material 2 can be formed on the anode current collector 1. Further, the composition of amorphous carbon and the elements of Sn or 4A, 5A, and 6A elements can be freely controlled within a wide range, and the thickness of the film can be easily controlled, and the negative electrode active material 2 can be easily and easily formed. On the anode current collector 1. Further, in the production method of the present invention, since a vapor deposition method is used, a film obtained by dispersing carbides of Sn or 4A, 5A, and 6A elements in amorphous carbon is formed on the negative electrode by vapor deposition. The current collector 1 was placed to obtain a negative electrode material 1 〇. Therefore, the step of applying the graphite carbon powder on the anode current collector, the step of drying the coated powder, and the coating and drying the powder on the anode current collection can be omitted in the current manufacturing method. The step of increasing the density. -14- 201110447 For vapor deposition, chemical vapor deposition (CVD: Chemical Vapor Deposition) or physical vapor deposition (PVD: Physical Vapor Deposition) can be used. CVD has plasma CVD. PVD has Vacuum evaporation method, sputtering method, ion plating method, arc ion plating method (AIP) 'laser ablation method, and the like. In particular, when thick film formation is required, a method of forming a film is required, and the AIP method is effective. For example, if the target is subjected to arc discharge as graphite, the graphite forms carbon atoms or ions to evaporate via the heat of the arc discharge, and amorphous carbon can be deposited on the surface of the negative electrode current collector. Further, in the A IP method using the graphite standard, "microparticles (macroscopic particles) of graphite from the surface of the target due to the arc discharge generated by carbon atoms or ions from the surface of the target; zm to several tens; t / m) It will fly out and deposit on the negative electrode current collector, and therefore, a film having a large graphite structure can be formed as compared with the sputtering method or the ion plating method. Therefore, a film which further occludes lithium can be formed. When the amorphous carbon film is formed by the AIP method, the Sn and the 4A, 5A, and 6A elements are evaporated in a vacuum chamber or a sputtering method to form Sn and 4A. An amorphous carbon film (negative electrode active material) of a carbide of a 5A or 6A element. In addition, when the electric discharge is performed by the AIP method, the hydrocarbon gas is decomposed and deposited on the surface of the negative electrode current collector by the arc discharge by introducing the hydrocarbon gas such as methane or ethylene. Therefore, the hydrocarbon gas can be further deposited on the surface of the negative electrode current collector. Pick up the film formation speed. Subsequently, an example of a method of manufacturing a negative electrode material 1 锂 for a lithium ion secondary battery using a sputtering method and a case where an a IP method is used will be described with reference to FIGS. 2 and 3', as long as a material using a vapor deposition method is used. It is not limited to these materials from -15 to 201110447. Here, a case where Sn (tin) and Zr (zirconium) are used will be described. Further, the configuration of the sputtering apparatus and the AIP-sputtering composite apparatus is not limited to the configuration shown in Figs. 2 and 3, and a known apparatus can be used. For the case of using the sputtering method, as shown in FIG. 2, first, a carbon target 22 having a thickness of 5 mm, a tin target 23, and a zirconium target 24 are provided in the chamber 21 of the sputtering device 20, and the length is 5 Ox. A copper foil 25 having a width of 50x and a thickness of 0.02 mm is provided on the substrate stage 26 in such a manner as to face the carbon target 22, the tin target 23, and the zirconium target 24. Subsequently, the pressure in the chamber 21 is 1x1 (the pressure is less than T3Pa, so that the inside of the chamber 21 is in a vacuum state. Thereafter, Ar gas is introduced into the chamber 21, so that the pressure in the chamber 21 becomes At 0.26 Pa, DC (direct current) is applied to the carbon target 22, the tin target 23, and the target 24 to generate plasma, and the carbon target 22, the tin target 23, and the target 24 are sputtered. Thus, a film is formed on the copper foil 25. A film (negative electrode active material) in which tin and pin carbide are dispersed in amorphous carbon, whereby a negative electrode material for a lithium ion secondary battery can be manufactured. For the case of using the AIP method, as shown in FIG. 3, first in AIP- In the chamber 31 of the sputtering composite device 30, a graphite target 32 having a diameter of 16 mm and a thickness of 16 mm, and a tin target 33 having a thickness of 6 mm and a thickness of 6 mm and a wrong target 34 are provided, and a copper foil 35 having a length of 50 Å and a width of 50 x 0.02 mm is provided. It is disposed on the surface of the revolving cylindrical substrate table 36. Subsequently, the pressure in the chamber 31 is lxl (the vacuum is not more than T3Pa, so that the chamber 31 is in a vacuum state. Thereafter) in the chamber 31. Ar gas was introduced to change the pressure in the chamber 31 to 0.26 Pa, and DC was applied to the graphite target 32, the tin target 33, and the zirconium target 34. Therefore, the graphite target 32 is subjected to arc discharge, the tin target 33 and the target 34 are subjected to glow discharge, the graphite is evaporated by the heat of the arc discharge, and the tin and zirconium are evaporated by sputtering of argon. Thus, a film (negative electrode active material) in which tin and chromium carbide are dispersed in amorphous carbon is formed on the copper foil 35. Thus, a negative electrode material for a lithium ion secondary battery can be produced. In the invention, in the range which does not adversely affect the above steps, for example, a negative electrode current collector cleaning step, a temperature adjustment step, and the like may be included between or before and after the above steps, and other steps may be included. The lithium ion secondary battery of the invention is a battery using the negative electrode material for a lithium ion battery described above. By using the negative electrode material of the present invention, a lithium ion secondary battery having a higher charge and discharge capacity, excellent cycle characteristics, and high-speed charge and discharge can be produced. The form of the lithium ion battery. The form of the lithium ion battery is a cylindrical type, a coin type, or a substrate-mounted film type. An angle type, a sheet type, or the like may be various types as long as the negative electrode material of the present invention can be used. The lithium ion secondary battery mainly has a charge transfer between the negative electrode material, the positive electrode material, the insulating material that insulates the electrode materials, and the auxiliary electrode material. The electrolyte solution and the battery case in which these are placed. Hereinafter, each structure will be described. <Anode material-17-201110447 The anode material of the present invention is used for the anode material, and the anode material is produced by the above invention. The method of the present invention is as follows: <The positive electrode material> The IE electrode material is not particularly limited, and a known material such as a lithium-containing oxide such as LiC〇02, LiNi〇2, or LiMn204 can be used. The method for producing the positive electrode material is not particularly limited, and a known method can be used. For example, an adhesive is added to the positive electrode materials of the & final type, and a conductive material 'solvent or the like is added as needed, and sufficiently kneaded, and then coated. It is produced by drying and pressing on a current collector such as an aluminum foil. <Isolation material> The separator is not particularly limited, and a known material such as a sheet of a porous body made of a polyolefin such as polypropylene or a separator such as a nonwoven fabric can be used. <Electrolyte> The electrolyte was injected into the battery case and sealed. When the electrolyte is charged and discharged, it is possible to move lithium ions generated by electrochemical reaction on the negative electrode material and the positive electrode material. As the solvent for the electrolyte of the electrolytic solution, a known aprotic or low dielectric constant solvent which can dissolve the lithium salt can be used. For example, the solvent may be used alone or in combination of a solvent such as ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, and propylene-18-201110447 nitrile. , tetrahydrofuran, r-butyrolactone, 2-methyltetrahydrofuran, anthracene, 3-dioxolane, 4-methyl-I,3-dioxolane, anthracene, 2-dimethoxyethane , hydrazine, 2_ diethoxyethane, diethyl ether, cyclobutyl hydrazine, methylcyclobutyl hydrazine, nitrocarbyl, N, N-dimethylformamide, dimethyl hydrazine and other solvents. The lithium salt used for the electrolyte of the electrolyte can be used, for example,
LiC104、LiAsF6、LiPF6、LiBF4、LiB(C6H5)4、LiCl ' CHJOsLi、CFsSC^Li等，其可以單獨使用該些鹽或可以 多個混合使用。 <電池盒> 電池盒放置上述的負極材料 '正極材料、隔離材料、 電解液等。 又，在製造鋰固體蓄電池、聚合鋰蓄電池的情形下， 經由與公知的正極材料' 聚合體電解質、固體電解質同時 使用本發明的鋰離子蓄電池用負極材料，可以製造安全性 高、高容量的蓄電池。 【實施方式】 [實施例] 以下，對於本發明的鋰離子蓄電池用負極材料，及其 製造方法’與鋰離子蓄電池，將以滿足本發明的要件的實 施例與不滿足本發明的要件的比較例相比較方式進行具體 說明。 -19- 201110447 [第一實施例] 經由以下的方法製造試料。 在如圖2所示的濺射裝置內的腔室內，設置4 100mm X厚度5mm的碳靶、錫靶（高純度化學股份有限公司製： 純度99.99%)，及銷靶（高純度化學股份有限公司製：純度 99.2%)，並將長50χ寬50x厚度0.02mm的銅箔（股份有限 公司nilaco製）依對向於碳靶、錫靶，及銷靶的方式設置 於基板台，依腔室內的壓力爲lxl(T3Pa以下的方式抽真 空，使腔室內處於真空狀態。其後，在腔室內導入 Ar氣 體，使腔室內的壓力變爲0.26Pa，對碳靶、錫靶，及锆靶 施加DC(直流）而產生等離子，濺射碳靶、錫靶，及鉻 靶。由此，在銅箔上成膜在非晶質碳中分散有錫及锆碳化 物的膜，從而製造鋰離子蓄電池用負極材料。 此時，經由調整施加於碳靶、錫靶，及锆靶的D C功 率，控制碳、錫、錐的組成，以製造表1所示的實施例 1 ~4及比較例1〜3、5的負極材料。又，膜厚全部設定爲1 从m。又，比較例4中使用膠黏劑將石墨塗佈在銅箔上， 並對其進行乾燥、擠壓而製作石墨負極材料。 又，以經由FIB-TEM觀察方式調查表1所示的實施 例1的負極材料的非晶質碳中的分散狀態。其結果是， FIB-TEM觀察時的碳以非晶質的相存在，觀察到在非晶質 碳中分散有2~5nm大小的錫粒子與5〜lOnm大小的碳化錐 的構造。 對依此方式所製得之試料，經由以下的方法進行充放 -20- .201110447 電特性評估。 [充放電特性評估] 配置所得的負極材料與在對極作爲正極材料的金屬 鋰，在兩電極材料間夾持聚丙烯製的多孔質體的隔離材 料。電解液，爲使用將lmol/Ι的6氟化磷酸鋰鹽以體積 比1對1溶解在碳酸亞乙酯與碳酸二甲酯的混合有機溶劑 而成的溶液，製造二極式電池單元的評估用電池單元。 又，圖4表示使用的評估用電池單元的構造的示意圖。 對該評估用電池單元，雰圍在室溫下，將充放電速度 設爲0.2C及10C兩種類，將截止電壓設爲0.005V、放電 時以1 .2V爲一循環，以10C下的充放電爲1〇〇循環方式 進行。而且，求得充放電速度0.2C及10C下的初次的放 電容量（初期放電容量）及充放電速度10C下的第100循環 次的容量維持率。又，容量維持率經由“第1 00循環次的 放電容量+初期放電容量X100”的計算式求得，10C下的 初期放電容量爲250mA/g以上，且第100循環次的容量 維持率在75%以上爲合格。在此，表示充放電速度的單位 C從放完電的狀態充滿電，或者從充滿電到放完電的時 間，1C表不用1小時充滿電，1 〇 C表示用1 /1 0小時=6 分鐘充滿電。 該些結果係如表1所示。又，表中的各元素的含量經 由以下的奧杰電子質譜分析（AES分析）求得。又，在表1 中，不滿足本發明的構成的材料及不滿足評估基準的材料 -21 - 201110447 爲於數値下方繪製下線表示。 (組成分析） 組成的分析’爲使用奧杰電子質譜分析（AES分析）實 施’而得膜中的元素濃度。在此，AES分析使用 PerkinElmer公司製PHI65 0掃描型奧杰電子質譜儀，對直 徑10ym的區域進行分析。在膜中存在1〇at%以下的成膜 時不可避免地混入的來自基板的銅及氧等雜質，將該些去 除’以（Sn的原子分率）/(Sn的原子分率+ Zr的原子分率+ C 的原子分率）爲膜中Sn組成，同樣，以（Zr的原子分 率）/(Sn的原子分率+Zr的原子分率+c的原子分率）及（C 的原子分率）/(Sn的原子分率+ Zr的原子分率+ C的原子分 率）分別作爲膜中Zr組成及C組成方式進行計算。 【表1】 膜 中組成(at%) 充放電速度 (0. 2C) 充放電速度(10C) C Sn Zr 初期放電容量 (mAh/g) 初期放電容量 (mAh/g〉 第100循環次的 容量維持率 (%) Η施例1 87 3 10 410 405 85 實施例2 85 】0 5 630 600 88 實施例3 55 30 15 520 510 85 實施例4 55 35 10 540 530 78 比較例1 45 45 10 600 595 10 比較例2 65 10 25 480 210 • 85 比較例3 89 10 丄 640 220 84 比較例4 100 0 0 270 240 70 比較例5 89.5 0.5 10 280 245 82 如表1所示，因實施例1 滿足本發明的要件，所以 與使用膠黏劑將石墨塗佈在銅箔上的比較例4相比，顯示 高的初期放電容量及第100循環次的容量維持率。 -22- 201110447 另一方面，由於在比較例1中，因Sn含量較多，故 初期的容量較高，但在循環試驗中劣化。在比較例2中， 由於Zr含量過多，而使碳化物過量形成，因此，充放電 速度提升時將會阻礙Li的擴散，其與使用膠黏劑將石墨 塗佈在銅箔上的比較例4顯示出更低的初期放電容量。比 較例3中，因Zr含.量小，所以顯示出充放電速度0.2 C之 較高的初期放電容量，但在充放電速度爲10C時，電子傳 導性惡化，因而初期容量降低。即，比較例2、3爲不能 高速充放電的材料。又，比較例5的Sn含量較少，所以 初期的充放電容量幾乎與比較例4沒有差別，而沒有增大 充放電容量的效果。 [第二實施例] 使用與第一實施例相同之濺射裝置成膜負極材料。但 是，將鉻靶變換爲其他的4A、5A、6A族元素的靶材並實 施成膜。其結果如表2所示。 【表2】 膜中組 充放電速度 (0. 20 充放電速度⑽:> 試料No. c Sn 4Λ, 5Λ, 6Λ族元素 初期放電容量 初期放電容量 第100循環次 的容量維持 (%) 靶材 種類 組成 (mAh/κ) (mAh/ii) 實施例5 80 10 Cr 10 650 635 87 實施例6 75 10 Ti 15 590 580 88 實施例7 85 10 Nh 5 620 610 85 實-施例8 83 10 Ta 7 640 630 86 實施例9 80 - 10 W 10 630 615 85 實施例1 0 87 10 Ϊ1Γ 3 630 580 83 如表2所示般，經由添加4A、5A、6A族元素，即使 -23- 201110447 充放電速度爲10C，也可以顯示與充放電速度0.2C同左 右的初期放電容量。又，經由添加Sn，可以使初期放電 容量較比較例4爲高，且Sn在本發明的範圍內進行調整 時，可得到良好之循環特性。 [第三實施例] 在第三實施例中，成膜方法爲，經由使用AIP法成膜 非晶質碳，使用濺射法同時成膜Sn與Cr，由此製造鋰離 子電池用負極材料。 在如圖3所示的AIP-濺射裝置的腔室內，設置φ lOOmmx厚度16mm的石墨標靶，及φ6英寸X厚度6mm的 錫靶（高純度化學股份有限公司製：純度99.99%)與鉻靶 (高純度化學股份有限公司製：純度99.9%)，並將長50x 寬50x厚度0.02mm的銅箔（股份有限公司nnaco製）設置 在公轉的圓筒狀的基板台表面，依腔室內的壓力爲ΙχΙΟ·3 Pa以下的方式抽真空，使腔室內處於真空狀態。其後， 在腔室內導入Ar氣體，使腔室內的壓力變爲〇.26Pa，對 石墨標靶、錫靶，及鉻靶施加DC(直流），使石墨標靶產 生電弧放電，使錫靶及鉻靶材產生輝光放電，使石墨經由 電弧放電的熱蒸發，並且使錫及鉻經由氬的濺射蒸發。由 此，在銅箔上成膜在非晶質碳中分散有錫及鉻碳化物的膜 (負極活性物質），製造鋰離子蓄電池用負極材料。此時的 電弧放電電流爲60A、濺射功率爲500W，施加於基板的 偏壓爲1 0V，進行1小時的成膜。 -24- 201110447 使用FIB-ΤΕΜ觀察方式調查該負極材料的非晶質碳 中的錫與鉻的分散狀態結果得知，碳爲在非晶質構造中含 有亂層構造的石墨的構造，在碳相中，觀察出分散有粒徑 5 ~ 1 0 n m大小的錫粒子與1 0〜1 5 n m大小的鉻碳化物粒子的 構造。又，用SEM觀察截面得知，負極材料的膜厚爲5 # m。又，Sn與Cr組成的分析與實施例2相同，以奧杰 電子質譜分析（AES分析）實施，所得Sn爲3at%、Cr爲 5 at % 〇 對依此方式所製得之試料，經由與第二實施例相同的 方法，進行充放電特性評估，求得充放電速度0.2C與 10C下的初期放電容量的測定與充放電速度10C下的500 循環充放電時的容量維持率。其結果，初期放電容量在 0.2C時爲415 mAh/g，在10C時爲410 mAh/g，容量維持 率爲83%。此種，對於用AIP法使非晶質碳成膜，且用濺 射法使Sn及Cr同時成膜而得的負極材料，與只成膜石墨 的比較例4相比，顯示高的初期放電容量，容量維持率也 顯示7 5 %以上。 從以上的結果可知，依據本發明的鋰離子蓄電池用負 極材料，可以得到兼具充分的充放電容量、優良的循環特 性且可高速充放電的鋰離子蓄電池。 以上對本發明的最佳的實施方式、實施例所進行之說 明，但本發明不限定於上述實施方式、實施例，其可以在 適合於本發明宗旨的範圍內寬泛地變更並改變，該些內容 均包含在本發明的技術範圍內。 -25- 201110447 【圖式簡單說明】 圖1爲表示本發明的鋰離子蓄電池用負極材料的構成 的剖面示意圖； 圖2爲用於製造本發明的鋰離子蓄電池用負極材料的 濺射裝置示意圖； 圖3爲用於製造本發明的鋰離子蓄電池用負極材料％ AIP-濺射複合裝置示意圖； 圖4爲表示在實施例中使用的評估用電池單元的構_ 示意圖。 【主要元件符號說明】 1 :負極集電體 2 :負極活性物質 10:鋰離子蓄電池用負極材料（負極材料） 20 :濺射裝置 21 :腔室 22 :碳靶 23 :錫靶 2 4 :銷靶 25 :銅箔 26 :基板台 30 :複合裝置 31 :腔室 -26- 201110447 3 2 :石墨標靶 3 3 :錫靶 3 4 :锆靶 35 :銅箔 3 6 :圓筒狀的基板台LiC104, LiAsF6, LiPF6, LiBF4, LiB(C6H5)4, LiCl'CHJOsLi, CFsSC^Li, etc., which may be used singly or in combination. <Battery case> The battery case is placed with the above-mentioned negative electrode material 'positive material, separator, electrolyte, and the like. Moreover, in the case of manufacturing a lithium solid state battery or a lithium ion secondary battery, it is possible to manufacture a battery having high safety and high capacity by using the negative electrode material for a lithium ion battery of the present invention together with a known positive electrode material 'polymer electrolyte or solid electrolyte. . [Embodiment] [Embodiment] Hereinafter, a negative electrode material for a lithium ion secondary battery of the present invention, a method for producing the same, and a lithium ion secondary battery, a comparison of an embodiment satisfying the requirements of the present invention with a condition not satisfying the present invention The example comparison method will be specifically described. -19-201110447 [First embodiment] A sample was produced by the following method. In a chamber in a sputtering apparatus as shown in FIG. 2, a carbon target of 4 100 mm X and a thickness of 5 mm, a tin target (manufactured by High Purity Chemical Co., Ltd.: purity: 99.99%), and a pin target (high-purity chemical limited stock) are provided. Company system: purity 99.2%), and a copper foil (manufactured by Nilaco Co., Ltd.) with a length of 50 inches wide and 50x thickness of 0.02 mm is placed on the substrate table in a manner corresponding to a carbon target, a tin target, and a pin target. The pressure is lxl (the vacuum is less than T3Pa, so that the chamber is under vacuum. Thereafter, Ar gas is introduced into the chamber to make the pressure in the chamber 0.26 Pa, and the carbon target, the tin target, and the zirconium target are applied. DC (direct current) generates plasma, and sputters a carbon target, a tin target, and a chromium target. Thus, a film in which tin and zirconium carbide are dispersed in amorphous carbon is formed on a copper foil to produce a lithium ion battery. A negative electrode material was used. At this time, the compositions of carbon, tin, and cone were controlled by adjusting the DC power applied to the carbon target, the tin target, and the zirconium target to produce Examples 1 to 4 and Comparative Example 1 shown in Table 1. 3, 5 of the negative electrode material. Also, the film thickness is set to 1 from m. Again, the comparative example In 4, graphite was coated on a copper foil with an adhesive, and dried and extruded to prepare a graphite negative electrode material. Further, the negative electrode material of Example 1 shown in Table 1 was examined by FIB-TEM observation. The dispersion state in the amorphous carbon. As a result, the carbon in the FIB-TEM observation exists in an amorphous phase, and it is observed that 2 to 5 nm of tin particles and 5 to lOnm are dispersed in the amorphous carbon. The structure of the size of the carbonized cone. The sample prepared in this manner was subjected to charge and discharge by the following method. -20-201110447 Electrical characteristics evaluation [Charge of charge and discharge characteristics] The obtained negative electrode material was used as the positive electrode at the opposite pole. a metal lithium material of a material, which is a separator for sandwiching a porous body made of polypropylene between two electrode materials. The electrolyte solution is dissolved in a volume ratio of 1 to 1 in a molar ratio of 1 mol/mol of lithium hexafluorophosphate phosphate. A battery cell for evaluation of a two-electrode cell is produced by mixing a solution of an ester and an organic solvent of dimethyl carbonate. Further, Fig. 4 is a schematic view showing the structure of the battery cell for evaluation used. The atmosphere is at room temperature, The charge/discharge rate was set to 0.2 C and 10 C, and the cutoff voltage was set to 0.005 V, the discharge was performed at 1.2 V for one cycle, and the charge and discharge at 10 C was performed for 1 cycle. Further, charge and discharge were obtained. The initial discharge capacity (initial discharge capacity) at a speed of 0.2 C and 10 C and the capacity retention rate at the 100th cycle of the charge/discharge rate of 10 C. Further, the capacity retention rate is "the discharge capacity of the 1st 00 cycle + the initial discharge" The calculation formula of the capacity X100" was obtained, and the initial discharge capacity at 10 C was 250 mA/g or more, and the capacity retention rate at the 100th cycle was 75% or more, which was acceptable. Here, the unit C indicating the charge and discharge rate was discharged. The state of electricity is fully charged, or from the time of full charge to discharge, the 1C meter is not fully charged for 1 hour, and 1 〇C means fully charged with 1 / 1 0 hours = 6 minutes. The results are shown in Table 1. Further, the content of each element in the table was determined by the following Auger electron mass spectrometry (AES analysis). Further, in Table 1, the material which does not satisfy the constitution of the present invention and the material which does not satisfy the evaluation criteria -21 - 201110447 are indicated by the lower line below the number. (Composition analysis) The analysis of the composition was carried out by using Aojie Electron Mass Spectrometry (AES analysis) to obtain the element concentration in the film. Here, the AES analysis was performed using a PHI65 0 scanning type Aojie electron mass spectrometer manufactured by PerkinElmer Co., Ltd. to analyze a region of 10 μm in diameter. In the film, impurities such as copper and oxygen which are inevitably mixed in the film formation when the film formation is 1 〇 at% or less are removed, and the atomic fraction (Sn atomic fraction) / (Sn atomic fraction + Zr) is removed. The atomic fraction + atomic fraction of C is the composition of Sn in the film, and similarly, the atomic fraction of (Zr) / (the atomic fraction of Sn + the atomic fraction of Zr + the atomic fraction of c) and (C The atomic fraction) / (the atomic fraction of Sn + the atomic fraction of Zr + the atomic fraction of C) is calculated as the Zr composition and the C composition of the film, respectively. [Table 1] Membrane composition (at%) Charge and discharge rate (0.2 C) Charge and discharge rate (10 C) C Sn Zr Initial discharge capacity (mAh/g) Initial discharge capacity (mAh/g) Capacity of the 100th cycle Maintenance rate (%) Example 1 87 3 10 410 405 85 Example 2 85 】0 5 630 600 88 Example 3 55 30 15 520 510 85 Example 4 55 35 10 540 530 78 Comparative Example 1 45 45 10 600 595 10 Comparative Example 2 65 10 25 480 210 • 85 Comparative Example 3 89 10 丄 640 220 84 Comparative Example 4 100 0 0 270 240 70 Comparative Example 5 89.5 0.5 10 280 245 82 As shown in Table 1, it is satisfied by Example 1. Since the requirements of the present invention are higher than those of Comparative Example 4 in which graphite is coated on a copper foil using an adhesive, it exhibits a high initial discharge capacity and a capacity retention rate at the 100th cycle. -22- 201110447 On the other hand, In Comparative Example 1, since the content of Sn was large, the initial capacity was high, but it deteriorated in the cycle test. In Comparative Example 2, since the Zr content was excessive, the carbide was excessively formed, and therefore, the charge and discharge rate was high. Lifting will hinder the diffusion of Li, which is compared with the use of adhesives to coat graphite on copper foil. In Example 3, the initial discharge capacity was lower. In Comparative Example 3, since the amount of Zr was small, the initial discharge capacity at a high charge/discharge rate of 0.2 C was exhibited, but at the charge and discharge rate of 10 C, electron conduction was observed. When the properties were deteriorated, the initial capacity was lowered. That is, Comparative Examples 2 and 3 were materials which could not be charged and discharged at a high speed. Further, in Comparative Example 5, the Sn content was small, so the initial charge and discharge capacity was almost the same as that of Comparative Example 4, and there was no difference. The effect of increasing the charge and discharge capacity. [Second embodiment] A negative electrode material was formed using the same sputtering apparatus as in the first embodiment. However, the chromium target was converted into a target of other 4A, 5A, and 6A elements and The film formation was carried out. The results are shown in Table 2. [Table 2] Charge and discharge rate in the film (0. 20 charge and discharge rate (10): > Sample No. c Sn 4Λ, 5Λ, 6 Λ element initial discharge capacity initial discharge Capacity maintenance at the 100th cycle of capacity (%) Target species composition (mAh/κ) (mAh/ii) Example 5 80 10 Cr 10 650 635 87 Example 6 75 10 Ti 15 590 580 88 Example 7 85 10 Nh 5 620 610 85 Real-Example 8 83 10 Ta 7 640 630 86 Implementation 9 80 - 10 W 10 630 615 85 Example 1 0 87 10 Ϊ1Γ 3 630 580 83 As shown in Table 2, by adding 4A, 5A, and 6A elements, even if the charge-discharge rate of -23-201110447 is 10C, An initial discharge capacity of about the same as the charge and discharge rate of 0.2 C was displayed. Further, by adding Sn, the initial discharge capacity can be made higher than that of Comparative Example 4, and when Sn is adjusted within the range of the present invention, good cycle characteristics can be obtained. [Third Embodiment] In the third embodiment, a film forming method is to form a negative electrode material for a lithium ion battery by simultaneously forming a film of amorphous carbon by using an AIP method and simultaneously forming a film of Sn and Cr by a sputtering method. In the chamber of the AIP-sputtering apparatus shown in FIG. 3, a graphite target of φ100 mmx thickness of 16 mm and a tin target of φ6 inch X thickness of 6 mm (manufactured by High Purity Chemical Co., Ltd.: purity 99.99%) and chromium were provided. Target (made by High Purity Chemical Co., Ltd.: purity: 99.9%), and a copper foil (manufactured by Nana Co., Ltd.) having a length of 50x and a width of 50x and a thickness of 0.02 mm was placed on the surface of a revolving cylindrical substrate table. The pressure is ΙχΙΟ·3 Pa or less, and the vacuum is applied to make the chamber vacuum. Thereafter, Ar gas is introduced into the chamber to change the pressure in the chamber to 〇.26 Pa, and DC (direct current) is applied to the graphite target, the tin target, and the chromium target to cause arc discharge of the graphite target to make the tin target and The chromium target produces a glow discharge that causes the graphite to evaporate via the heat of the arc discharge and causes the tin and chromium to evaporate via sputtering of argon. As a result, a film (negative electrode active material) in which tin and chromium carbide are dispersed in amorphous carbon is formed on the copper foil to produce a negative electrode material for a lithium ion secondary battery. At this time, the arc discharge current was 60 A, the sputtering power was 500 W, and the bias voltage applied to the substrate was 10 V, and film formation was performed for 1 hour. -24- 201110447 The dispersion state of tin and chromium in amorphous carbon of the negative electrode material was investigated by FIB-ΤΕΜ observation method. As a result, it was found that carbon is a structure containing graphite in a disordered structure in an amorphous structure, in carbon. In the phase, the structure in which tin particles having a particle size of 5 to 10 nm and chromium carbide particles having a size of 10 to 15 nm were dispersed were observed. Further, it was found by SEM observation that the film thickness of the negative electrode material was 5 # m. Further, the analysis of the composition of Sn and Cr was carried out in the same manner as in Example 2, and was carried out by Aojie electronic mass spectrometry (AES analysis), and the obtained Sn was 3 at% and Cr was 5 at %. The sample prepared in this manner was passed through In the same manner as in the second embodiment, the charge and discharge characteristics were evaluated, and the initial discharge capacity at a charge and discharge rate of 0.2 C and 10 C and the capacity retention rate at the charge and discharge rate of 10 C at 500 cycles of charge and discharge were determined. As a result, the initial discharge capacity was 415 mAh/g at 0.2 C, 410 mAh/g at 10 C, and the capacity retention rate was 83%. In this way, the negative electrode material obtained by forming amorphous film by AIP method and simultaneously forming Sn and Cr by sputtering method shows high initial discharge compared with Comparative Example 4 in which only graphite is formed. Capacity and capacity retention rate also show above 75%. As is apparent from the above results, according to the negative electrode material for a lithium ion secondary battery of the present invention, a lithium ion secondary battery which has both sufficient charge and discharge capacity and excellent cycle characteristics and can be charged and discharged at a high speed can be obtained. The preferred embodiments and examples of the present invention have been described above, but the present invention is not limited to the above-described embodiments and examples, and may be widely changed and changed within the scope of the gist of the present invention. All are included in the technical scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing a configuration of a negative electrode material for a lithium ion secondary battery of the present invention; FIG. 2 is a schematic view showing a sputtering apparatus for producing a negative electrode material for a lithium ion secondary battery of the present invention; Fig. 3 is a schematic view showing a % AIP-sputtering composite device for producing a negative electrode material for a lithium ion secondary battery of the present invention; and Fig. 4 is a view showing a configuration of a battery cell for evaluation used in the embodiment. [Description of main component symbols] 1 : Negative electrode current collector 2 : Negative electrode active material 10 : Anode material for lithium ion battery (negative electrode material) 20 : Sputtering device 21 : Chamber 22 : Carbon target 23 : Tin target 2 4 : Pin Target 25: Copper foil 26: Substrate table 30: Composite device 31: Chamber-26-201110447 3 2: Graphite target 3 3: Tin target 3 4: Zirconium target 35: Copper foil 3 6 : Cylindrical substrate stage