201110446 六、發明說明： 【發明所屬之技術領域】 本發明係有關用於鋰離子蓄電池的鋰離子蓄電池用負 極材料、其製造方法、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】 鋰離子蓄電池主要由負極材料、正極材料、將這些電 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、收容它們的電池盒所構成。而且，鋰離子蓄電池用 負極材料是在由銅箔或銅合金箔所構成的集電材料上塗敷 負極活性物質而成的。作爲負極活性物質，一般使用石墨 系碳材料。 近年來，由於行動裝置的小型化及高性能化，對所搭 載之蓄電池的能量密度的要求越來越高。其中，鋰離子蓄 電池與鎳一鎘蓄電池或鎳一氫蓄電池相比，顯示高電壓、 高能量密度（充放電容量），因此，開始作爲前述行動裝 置的電源而被廣泛使用。 另外’隨著環境意識的提高，希望從現在的使用化石 燃料的汽車朝向co2排出量少的電動汽車、混合動力汽車 轉變’作爲搭載於上述設備的電池，對鋰離子蓄電池的期 待提高β 作爲搭載於電動汽車及混合動力汽車的電池所追求的 胃'性’可以列舉除能量密度高（每次充電的續航距離增大 I S1 -5- 201110446 ’需要充電的次數減少）、循環特性良好（延長電池的壽 命）之外，充放電速度爲高速。在此，所謂循環特性是指 ，即使反覆充放電的循環，也不會使負極活性物質劣化（ 剝離、脫落等），充放電容量不會降低的性質。 其中，充放電速度爲搭載於汽車的電池中所特別追求 的性能，若充電速度快，則即使在儲存於電池之能量用盡 的情況下，也可以用短的充電時間返回滿充電的狀態。另 外，在充電速度快的情況下，使用再生制動時作爲熱而失 去的能量減少，因此，可以有效地再利用能量，也關係到 續航距離的增大。另一方面，快的放電速度則關係到良好 的加速性能。 通常，在搭載於電動汽車的電池中，目標是可以最低 爲10C速率（10C速率爲可以以6分鐘滿充放電的電流）左 右之電流的充放電。 因此，作爲顯示高充放電容量的負極活性物質，針對 Si、Ge、Ag、In、Sn及Pb等之可以與鋰合金化的金屬進行 硏究。例如在專利文獻1提案將顯示石墨系碳材料之大約 2.5倍的993 m Ah/g這樣的理論充放電容量的Sn蒸鍍在集電 體上的負極材料。但是，由於Sn在鋰離子的充放電時（與 鋰的合金化、鋰的釋放）反覆體積膨脹和收縮，Sn自集電 體剝離而電阻增加，或Sn自身破裂而導致Sn之間的接觸電 阻增加，因此，結果存在充放電容量大幅降低這樣的問題 〇 以解決該問題的方案而言，爲了緩和負極活性物質的 -6- 201110446 體積變化’在專利文獻2中提案將Sn等的金屬奈米結晶的 表面進行碳塗敷的金屬奈米結晶複合體、或將用碳塗敷層 連結金屬奈米結晶複合體的金屬奈米結晶複合體與聚二氟 乙烯（PVDF )等結合材料與炭黑混合並塗佈在銅集電體 上後，進行真空燒結的負極材料。 [先前技術文獻] [專利文獻] 專利文獻1:日本特開2002-1 1 〇15 1號公報 專利文獻2:日本特開20〇7-3〇5569號公報 【發明內容】 [發明所欲解決之課題] 但是，在專利文獻2的負極材料中，由於吸留鋰的金 屬結晶爲奈米尺寸，所以鋰吸留引起的體積變化小，可以 維持高充放電容量’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’即使添加了炭黑，作爲負極電極材 料的導電性也會變差。因此，在需要如汽車那樣進行高速 充放電的用途中，存在不能流過大電流，充放電容量降低 這樣的問題。 本發明係鑒於前述問題而提供一種兼具高充放電容量 、良好的循環特性、以及快速的充放電速度的鋰離子蓄電 池用負極材料、及其製造方法、以及使用鋰離子蓄電池用 負極材料的鋰離子蓄電池。[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] A lithium ion secondary battery is mainly composed of a negative electrode material, a positive electrode material, an insulating material that insulates these electrode materials, an electrolyte that moves electric charges between auxiliary electrode materials, and a battery case that houses them. Further, the negative electrode material for a lithium ion secondary battery is obtained by coating a negative electrode active material on a current collector made of a copper foil or a copper alloy foil. As the negative electrode active material, a graphite-based carbon material is generally used. In recent years, due to the miniaturization and high performance of mobile devices, the energy density of the battery to be mounted has become higher and higher. Among them, a lithium ion battery exhibits a high voltage and a high energy density (charge and discharge capacity) as compared with a nickel-cadmium battery or a nickel-hydrogen battery. Therefore, it has been widely used as a power source for the above-mentioned mobile device. In addition, with the improvement of the environmental awareness, it is expected to change from the current use of fossil fuel vehicles to electric vehicles and hybrid vehicles with a small amount of co2 emissions. The gastric 'sexuality' pursued by batteries for electric vehicles and hybrid vehicles can be enumerated as high energy density (increasing the cruising distance per charge I S1 -5 - 201110446 'reduced number of charging times), and good cycle characteristics (extended) In addition to the life of the battery, the charge and discharge speed is high. Here, the cycle characteristic means that the negative electrode active material does not deteriorate (peeling, peeling, etc.) even if the cycle of charge and discharge is repeated, and the charge/discharge capacity does not deteriorate. Among them, the charge/discharge speed is a performance that is particularly sought after in a battery mounted in an automobile. If the charging speed is fast, the battery can be returned to the fully charged state with a short charging time even when the energy stored in the battery is used up. Further, in the case where the charging speed is fast, the energy lost as heat during regenerative braking is reduced, so that energy can be effectively reused, which is also related to an increase in the cruising distance. On the other hand, a fast discharge rate is associated with good acceleration performance. Generally, in a battery mounted on an electric vehicle, the target is charging and discharging of a current of a minimum of 10C (a current of 10C can be fully charged and discharged for 6 minutes). Therefore, as a negative electrode active material exhibiting a high charge and discharge capacity, a metal which can be alloyed with lithium, such as Si, Ge, Ag, In, Sn, and Pb, is investigated. For example, Patent Document 1 proposes a negative electrode material in which Sn of a theoretical charge and discharge capacity such as 993 m Ah/g of about 2.5 times of a graphite-based carbon material is vapor-deposited on a current collector. However, since Sn recharges and discharges during lithium ion charge and discharge (alloying with lithium, release of lithium), Sn is peeled off from the current collector and resistance increases, or Sn itself ruptures to cause contact resistance between Sn. As a result, there is a problem that the charge and discharge capacity is greatly reduced. In order to solve the problem, in order to alleviate the volume change of the negative electrode active material -6-201110446, it is proposed in Patent Document 2 to use a metal nano such as Sn. a metal nanocrystal composite in which a carbonized surface is carbonized, or a metal nanocrystal composite in which a metal nanocomposite is bonded by a carbon coating layer, and a bonding material such as polytetrafluoroethylene (PVDF) and carbon black. After mixing and coating on the copper current collector, vacuum-sintered negative electrode material was performed. [Prior Art Document] [Patent Document] Patent Document 1: JP-A-2002-1 1 〇 15 1 pp. Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. Hei. However, in the negative electrode material of Patent Document 2, since the metal crystal occluding lithium is in a nanometer size, the volume change due to lithium occlusion is small, and high charge and discharge capacity can be maintained, but in order to use a bonding material for metal The bonding between the nanocrystal composites', even if carbon black is added, the conductivity as a negative electrode material is deteriorated. Therefore, in applications requiring high-speed charge and discharge as in automobiles, there is a problem that a large current cannot flow and the charge and discharge capacity is lowered. The present invention provides a negative electrode material for a lithium ion secondary battery having high charge and discharge capacity, good cycle characteristics, and rapid charge and discharge speed, and a method for producing the same, and lithium using a negative electrode material for a lithium ion secondary battery, in view of the foregoing problems Ion battery.
[[SB 201110446 [解決課題之手段] 作爲用於解決前述課題的手段，本發明的鋰離子蓄電 池用負極材料，其係用於鋰離子蓄電池的鋰離子蓄電池用 負極材料，其特徵爲，前述鋰離子蓄電池用負極材料係將 Sn和Ag分散於非晶質碳中的負極活性物質形成於負極集電 體上，前述負極活性物質之非晶質碳的含量爲5 Oat%以上 ，Sn含量和Ag含量之比（Sn/Ag)爲0.5〜4。 根據這樣的構成，Sn及Ag不與碳進行合金化而以奈米 粒子尺寸分散於非晶質碳中。而且，Sn係吸留Li而引起大 的體積變化，但由於分散於非晶質碳膜中，所以藉由非晶 質碳的結晶構造中的sp3結合可緩和體積變化。另外，非 晶質碳的含量在規定範圍內，因此Sn的體積變化可進一步 緩和。因此，充放電容量（比質量容量或比體積容量）提 高，同時，負極活性物質自集電體的剝離、破裂、微粉化 (循環特性良好）被抑制。而且，分散於非晶質碳中的Ag 與Li之間不形成金屬間化合物，但由於具有固溶大量Li之 相’因此，具有提高於負極活性物質中的Li離子之擴散速 度的作用’同時’由於是金屬元素，因此，具有提高負極 活性物質的電子傳導性的作用。另外，由於以與Sn含量的 比所規定的Ag含量在規定範圍內，因此Li離子的擴散速度 及電子傳導性進一步提高。因此，具有高充放電容量、良 好的循環特性 '同時，其充放電速度提高。 本發明的鋰離子蓄電池用負極材料的製造方法爲前述 的鋰離子蓄電池用負極材料的製造方法，其特徵爲，將前[BSB 201110446 [Means for Solving the Problem] 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, which is characterized in that the lithium is used as a means for solving the above problems. The negative electrode material for an ion storage battery is formed on a negative electrode current collector in which a negative electrode active material in which Sn and Ag are dispersed in amorphous carbon, and the amorphous carbon content of the negative electrode active material is 5 Oat% or more, Sn content and Ag. The content ratio (Sn/Ag) is 0.5 to 4. According to such a configuration, Sn and Ag are not alloyed with carbon and dispersed in amorphous carbon in a nanoparticle size. Further, Sn absorbs Li and causes a large volume change. However, since it is dispersed in the amorphous carbon film, the volume change can be alleviated by sp3 bonding in the crystal structure of amorphous carbon. Further, since the content of the non-crystalline carbon is within the predetermined range, the volume change of Sn can be further alleviated. Therefore, the charge/discharge capacity (specific mass capacity or specific volume) is improved, and the negative electrode active material is suppressed from peeling, cracking, and micronization of the current collector (good cycle characteristics). Further, an intermetallic compound is not formed between Ag and Li dispersed in amorphous carbon, but has a function of increasing the diffusion rate of Li ions in the negative electrode active material by having a solid phase of a large amount of Li. 'Because it is a metal element, it has an effect of improving the electron conductivity of the negative electrode active material. Further, since the Ag content defined by the ratio of the Sn content is within a predetermined range, the diffusion rate and electron conductivity of Li ions are further improved. Therefore, it has a high charge and discharge capacity and good cycle characteristics. At the same time, its charge and discharge speed is improved. A 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, characterized in that
-8- 201110446 述負極活性物質藉由氣相沉積法形成於負極集電體上。 根據這樣的製造方法，藉由使用氣相沉積法，將Sn及-8- 201110446 The negative electrode active material is formed on the negative electrode current collector by a vapor phase deposition method. According to such a manufacturing method, Sn and
Ag有效地分散於非晶質碳中。另外，非晶質碳、Sn及Ag 的組成的控制及負極活性物質之被膜厚度的控制變得容易 〇 另外，本發明的鋰離子蓄電池用負極材料的製造方法 ，其特徵爲，前述負極活性物質之非晶質碳的形成係使用 石墨靶且藉由電弧離子電鏟法進行。 根據這樣的製造方法，因成膜速度快，故可以實現厚 膜化，另外，藉由形成石墨結構多的膜，而容易吸留鋰。 本發明的鋰離子蓄電池，其特徵爲，使用前述的鋰離 子蓄電池用負極材料。 根據這樣的構成，藉由使用本發明的鋰離子蓄電池用 負極材料，可以形成具有高充放電容量和良好的循環特性 、以及高速充放電特性優良的鋰離子蓄電池。 [發明效果] 根據本發明的鋰離子蓄電池用負極材料，藉由提高具 有高充放電容量和良好的循環特性的負極活性物質之負極 活性物質中的Li離子的擴散速度和負極活性物質的電子傳 導性，可以得到充放電速度也優異的鋰離子蓄電池用負極 材料。 根據本發明的鋰離子蓄電池用負極材料的製造方法， 可以製造兼具高充放電容量、良好的循環特性、以及快速 201110446 的充放電速度的鋰離子蓄電池用負極材料。另外，藉由使 用氣相沉積法’可以在負極集電體上容易且簡便地形成負 極活性物質。而且，藉由使用石墨靶的電弧離子電鍍法， 可以使充放電容量進一步提高。 本發明的鋰離子蓄電池不僅具有高充放電容量、良好 的循環特性，而且在高速充放電時可以發揮高的容量❶ 【實施方式】 接著，參照圖式針對本發明的鋰離子蓄電池用負極材 料、及其製造方法'以及鋰離子蓄電池進行詳細說明。 《鋰離子蓄電池用負極材料》 如第1圖所示，本發明的鋰離子蓄電池用負極材料（ 以下’亦適合稱爲負極材料）10係具有負極集電體1和形 成在負極集電體1上的負極活性物質2。以下，將針對各構 成進行說明。 <負極集電體> 負極集電體1的材質係需要具有耐受負極活性物質2膨 脹之應力的機械特性。在拉伸大的（塑性變形容易、耐力 小）材質中，發生伴隨負極活性物質2的膨脹，一起產生 拉伸（塑性變形）的褶皺或彎折等。從這樣的理由來看， 作爲負極集電體1的材質，一般使用銅、銅合金、鎳、不 銹鋼等金屬，其中，從容易對薄膜加工這點和成本點而言 -10- 201110446 ’以耐力大、斷裂拉伸爲2%左右以下這樣的銅箔或銅合金 箔爲佳。另外，抗拉強度越高越好，以至少700N/mm2以上 的抗拉強度爲佳。在這點上，比起電解銅箔以軋製銅合金 箔爲佳。作爲這樣高強度的銅合金箔，例如可以列舉使用 含有Ni或Si之所謂的科森系銅合金的箔。 負極集電體1的厚度以1〜50#m爲佳。在厚度不足1 /zm時，負極集電體1不能耐受在負極集電體〗表面形成負 極活性物質2時的應力，有在負極集電體1上產生斷裂或龜 裂之虞。另一方面，在厚度超過50# m時，製造成本增加 ，另外，有電池大型化之虞。另外，更佳爲1〜30/zm。 <負極活性物質> 負極活性物質2爲於非晶質碳中分散Sn和Ag，且非晶 質碳的含量爲50at%以上，Sn含量和Ag含量之比（Sn/ Ag )爲0.5〜4。而且，在負極活性物質2中存在成膜時不可 避免地混入的來自負極集電體的雜質（銅及氧等），但在 本發明中，除去該雜質而算出C、Ag、Sn含量。因此，負 極活性物質2係由C、Sn及Ag所構成，C的含量爲50at%以 上，Sn的含量和Ag的含量之合計爲不足50at%。 [非晶質碳] 非晶質碳具有碳的sp2和sp3結合，例如顯示像金剛石 碳那樣的結晶構造。則述構造中的碳的sp3結合（碳矩陣 )發揮抑制充放電時之分散於非晶質碳中的Sn體積變化的 -11 - 201110446 作用。另外，從充放電容量增大這點而言，非晶質碳以具 有吸留石墨構造等之鋰的構造較佳。 負極活性物質2中的非晶質碳的含量爲5 0 at%以上。藉 由在非晶質碳中使Sn及Ag分散，可以實現充放電容量、循 環特性及高速充放電特性的提高，特別是藉由將非晶質碳 的含量設定在前述範圍內，即使反覆進行充放電後，由於 可藉由碳矩陣緩和Sn的體積變化，所以可得到良好的循環 特性。在非晶質碳的含量不足50at%時，不能藉由碳矩陣 使Sii的體積變化緩和，循環特性惡化。較佳爲55at%以上 ，更佳爲60at%以上。 [Sn及 Ag] 由於Sn及Ag爲可以與鋰合金化且熔點低的金屬，因此 不與熔點高的碳合金化而分散於非晶質碳中。而且，Sri的 含量和Ag的含量的合計爲不足50at%，其比設定爲（Sn/Ag )爲0.5〜4。 藉由將Sn和Ag分散在負極活性物質2中占50at%以上的 非晶質碳中（分散爲奈米晶簇狀），且將Sn/ Ag設定爲 0.5〜4，與以往的負極材料相比，可以形成充放電容量及 循環特性優良，且可以高速充放電的負極材料1〇。 藉由在負極活性物質2的非晶質碳中將Sn及Ag分散， 可以實現充放電容量和高速充放電特性的提高’特別是藉 由將Sn/Ag設定爲0.5〜4，可以進一步提高充放電容量和 高速充放電特性。在此，S η係藉由吸留Li而使充放電容量 -12- 201110446 提高。而且，Ag係藉由提高Li離子的擴散速度及負極活性 物質2的電子傳導性而使高速充放電特性提高。 在負極活性物質2中的Sn/Ag超過4時，相對於擔當Li 吸留的Sn，擔當Li離子的擴散及電子的傳導之Ag的量變少 ，因此，使充放電速度提高的效果減少。另外，在Sn/ Ag 不足0.5時，負極活性物質2中的擔當Li吸留的Sn之比例減 少，因此充放電容量減少。 在此，分散於非晶質碳中的Sn和Ag的粒徑以0.5〜 100nm爲佳。藉由使Sn和Ag的粒徑分散爲0.5〜100nm的奈 米晶簇狀，可以使充放電時的Sn和Ag的體積變化進一步緩 和，可以實現充放電容量和高速充放電特性的提高。 S η和Ag的粒徑的控制係藉由控制負極活性物質2中非 晶質碳與金屬（Sn及Ag )的組成來進行。另外，組成的控 制可以藉由在負極集電體1上形成負極活性物質2時的成膜 條件來控制。另外，Sn和Ag的粒徑的測定，可以藉由FIB-TEM觀察或薄膜X (愛克斯）射線衍射所觀察的金屬之衍 射線強度的半輻値爲基礎進行。而且，負極活性物質2的 組成的分析可以藉由歐傑電子譜儀分析（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，將 特徵爲在占50at%以上的非晶質碳中分散Sn和Ag .，且Sn/ Ag的比爲0.5〜4的負極活性物質2，藉由氣相沉積法形成在 -13- 201110446 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工序和負 極活性物質形成工序’藉由負極集電體形成工序形成負極 集電體1後，藉由負極活性物質形成工序，將特徵爲在占 5(^%以上的非晶質碳中分散311和八§，且811/人8的比爲〇.5 〜4的負極活性物質2’藉由氣相沉積法形成在該負極集電 體1上。以下，針對各工序進行說明。 <負極集電體形成工序> 負極集電體形成工序爲形成負極集電體1的工序。即 ，是爲了形成負極活性物質2而準備負極集電體1的工序。 作爲負極集電體1，如前述，只要使用公知的負極集電體1 即可。另外，藉由負極集電體形成工序，可以實施負極集 電體1的變形的矯正及硏磨等。 <負極活性物質形成工序> 負極活性物質形成工序爲將S η和Ag藉由氣相沉積法分 散於占50at %以上的非晶質碳中，同時，使藉由向前述非 晶質碳中的Sn和Ag的分散形成的負極活性物質2，形成在 負極集電體1上的工序。 藉由使用氣相沉積法，將Sn和Ag在占50at%以上的非 晶質碳中以奈米晶簇狀地分散，同時，可以在負極集電體 1上形成負極活性物質2。另外，可以將非晶質碳及金屬（ Sn及Ag)的組成自由控制在廣範圍內，同時，也可以容易 -14- 201110446 地控制被膜（負極活性物質2 )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。被膜的厚度以 0.1 〜100/z m爲佳。 另外，在本發明的製造方法中’由於使用氣相沉積法 ，因此，使將Sri及Ag分散在非晶質碳中而成的膜（負極活 性物質2)藉由蒸鍍形成在負極集電體1上而得到負極材料 10。因此，可以省略以往的製造方法中的將石墨質碳粉末 塗佈在負極集電體上的工序、使塗佈的粉末乾燥的工序、 及將塗佈並乾燥的粉末按壓在負極集電體而提高密度的工 序。 作爲氣相沉積法，可以使用化學氣相沉積法（CVD : Chemical Vapor Deposition法）或物理氣相沉積法（PVD :Physical Vapor Deposition法）等，作爲 CVD 法有等離子 CVD法’作爲PVD法有真空蒸鍍法' 濺射法、離子電鍍法 、電弧離子電鍍法（AIP )、雷射消融法等。特別是需要 厚膜化時’需要使用成膜速度快的手法，對此，AIP法有 效。例如’右將祀作爲石墨而進行電弧放電，則石墨會藉 由電弧放電的熱而作爲碳原子或離子蒸發，可以在負極集 電體表面堆積非晶質碳。進而，在使用石墨靶的AIP法中 ’由於除電弧放電會產生的來自靶表面的碳原子或離子以 外，從數到數十^111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，與濺射法或離子電 鍍法相比’可以形成石墨構造多的膜。因此，可以形成更 吸留鋰的膜。在由該AIP法形成非晶質碳膜的同時，在同 -15 - 201110446 一腔室內，若將Sn及Ag藉由真空蒸鍍法或濺射法進行蒸發 ，則可以形成含有Sn及Ag的非晶質碳膜（負極活性物質2 )。另外，在以AIP法進行放電時，邊導入甲烷或乙烯等 烴氣體邊實施時，藉由電弧放電，這些烴氣體分解而作爲 非晶質碳膜堆積在負極集電體表面，因此，可以使成膜速 度進一步提高。 接著，參照第2、3圖，針對使用濺射法的情況及使用 AIP法的情況之鋰離子蓄電池用負極材料10的製造方法的 一例進行說明，只要是使用氣相沉積法的材料，則不限定 於這些材料。另外，濺射裝置20及AIP -濺射複合裝置30 的構成係不限定以第2、3圖所示者，可以使用公知的裝置 〇 針對於使用濺射法的情況，如第2圖所示，首先在濺 射裝置20的腔室21內，設置<pl〇〇mmx厚度5mm的碳靶23及 錫靶22、及銀靶24，並將長50x寬50χ厚度0.02mm的基板（ 銅箔）25按照對向於碳靶23、錫靶22、及銀靶24的方式進 行設置。接著，按照腔室21內的壓力爲lxl(T3Pa以下的方 式抽成真空’使腔室21內處於真空狀態。其後，於腔室21 內導入Ar氣體’使腔室21內的壓力變爲〇.26Pa，對各靶材 施加DC (直流）而產生等離子，將碳靶23、錫靶22、及銀 靶2 4進行濺射。藉此，在作爲負極集電體的基板（銅箔） 25上將在非晶質碳中分散有錫及銀的膜（負極活性物質） 予以成膜。由此，可以製造鋰離子蓄電池用負極材料。 針對於使用AIP法的情況，如圖3所示，首先在AIP — -16- 201110446 濺射複合裝置30的腔室31內設置φ lOOmmx厚度l6mm的石 墨靶32、及φ6英寸X厚度6mm的銀靶33及錫靶34，並將長 50x寬50χ厚度〇.〇2mm的銅箔35設置在公轉的圓筒狀的基板 台36表面。接著，按照腔室31內的壓力爲1><10_3?&以下的 方式抽成真空，使腔室31內處於真空狀態。其後，向腔室 31內導入Ar氣體，使腔室31內的壓力變爲0.26Pa，對石墨 靶32、錫靶34、及銀靶33施加DC (直流）而使石墨靶32產 生電弧放電，使銀靶33及錫靶34產生輝光放電，使石墨藉 由電弧放電的熱蒸發，並且使錫及銀藉由氣的灘射蒸發。 藉此，在作爲負極集電體的銅箔3 5上將在非晶質碳中分散 有錫及銀的膜（負極活性物質）予以成膜。因此，可以製 造鋰離子蓄電池用負極材料。 另外，每次進行本發明時，在不對前述各工序產生不 良影響的範圍內，在前述各工序之間或前後也可以包含例 如負極集電體清洗工序、溫度調整工序等，也可包含其他 工序。 《鋰離子蓄電池》 本發明的鋰離子蓄電池爲使用前述記載的鋰離子蓄電 池用負極材料的電池。藉由使用本發明的負極材料，可以 製造具有高充放電容量、良好的循環特性，而且高速充放 電特性優良的鋰離子蓄電池。 《鋰離子蓄電池的形態》 . 201110446 作爲鋰離子蓄電池的形態，例如可以舉出圓筒型、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，則可以爲各種形態。 鋰離子蓄電池主要由負極材料、正極材料、將這些電 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、收容這些的電池盒所構成。以下，針對各構成進行 說明。 <負極材料> 負極材料使用前述的本發明的負極材料，另外，該負 極材料藉由前述發明的製造方法進行製造。 <正極材料> 正極材料沒有特別的限定，可以使用公知的材料，例 如LiCo02、UNi02、LiMn204等含鋰氧化物。對正極材料 的製造方法也沒有特別限定，除了可以利用公知的方法， 例如對粉末狀的這些正極材料添加黏合劑之外，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> 針對隔離材料沒有特別限定，可以使用公知的材料， 例如聚乙嫌、聚丙烯等聚烯烴作爲原料的多孔質體的片材 或不織布等的隔離材料。Ag is effectively dispersed in amorphous carbon. In addition, the control of the composition of the amorphous carbon, the Sn, and the Ag, and the control of the thickness of the negative electrode active material are facilitated. Further, the method for producing a negative electrode material for a lithium ion secondary battery of the present invention is characterized in that the negative active material is The formation of amorphous carbon is carried out by means of an arc ion shovel method using a graphite target. According to such a production method, since the film formation rate is high, it is possible to achieve a thick film formation, and it is easy to store lithium by forming a film having a large graphite structure. The lithium ion secondary battery of the present invention is characterized in that the above negative electrode material for a lithium ion secondary battery is used. According to such a configuration, by using the negative electrode material for a lithium ion secondary battery of the present invention, a lithium ion secondary battery having high charge and discharge capacity, excellent cycle characteristics, and excellent high-rate charge and discharge characteristics can be formed. [Effect of the Invention] According to the negative electrode material for a lithium ion secondary battery of the present invention, the diffusion rate of Li ions in the negative electrode active material of the negative electrode active material having high charge and discharge capacity and good cycle characteristics and the electron conduction of the negative electrode active material are improved. It is possible to obtain a negative electrode material for a lithium ion secondary battery which is excellent in charge and discharge speed. According to the method for producing a negative electrode material for a lithium ion secondary battery of the present invention, a negative electrode material for a lithium ion secondary battery having both a high charge and discharge capacity, good cycle characteristics, and a rapid charge and discharge rate of 201110446 can be produced. Further, the negative electrode active material can be easily and easily formed on the negative electrode current collector by using the vapor deposition method. Further, the charge and discharge capacity can be further improved by the arc ion plating method using a graphite target. The lithium ion secondary battery of the present invention has a high charge and discharge capacity and good cycle characteristics, and can exhibit a high capacity at the time of high-speed charge and discharge. [Embodiment] Next, a negative electrode material for a lithium ion secondary battery of the present invention will be described with reference to the drawings. And its manufacturing method' and lithium ion battery are described in detail. <<Negative Electrode Material for Lithium Ion Batteries>> As shown in Fig. 1, the negative electrode material for a lithium ion secondary battery of the present invention (hereinafter also referred to as "negative electrode material") has a negative electrode current collector 1 and a negative electrode current collector 1 The negative electrode active material 2 on the upper side. Hereinafter, each configuration will be described. <Anode Current Collector> The material of the anode current collector 1 is required to have mechanical properties that are resistant to the stress of expansion of the anode active material 2. In the material having a large tensile force (easily plastic deformation and low endurance), wrinkles or bends accompanying the expansion of the negative electrode active material 2 and stretching (plastic deformation) occur. From such a reason, as the material of the negative electrode current collector 1, metals such as copper, copper alloy, nickel, and stainless steel are generally used, and from the point of view of easy processing of the film and the cost point, -10-201110446 'endurance A copper foil or a copper alloy foil having a large and a tensile elongation of about 2% or less is preferred. Further, the higher the tensile strength, the better, and the tensile strength of at least 700 N/mm2 or more is preferred. In this regard, it is preferred to roll the copper alloy foil compared to the electrolytic copper foil. As such a high-strength copper alloy foil, for example, a foil using a so-called Corson-based copper alloy containing Ni or Si can be used. The thickness of the negative electrode current collector 1 is preferably 1 to 50 #m. When the thickness is less than 1 / zm, the negative electrode current collector 1 cannot withstand the stress when the negative electrode active material 2 is formed on the surface of the negative electrode current collector, and may cause cracks or cracks in the negative electrode current collector 1. On the other hand, when the thickness exceeds 50 # m, the manufacturing cost increases, and there is a problem that the battery is enlarged. Further, it is more preferably 1 to 30/zm. <Negative Electrode Active Material> The negative electrode active material 2 is obtained by dispersing Sn and Ag in amorphous carbon, and the content of amorphous carbon is 50 at% or more, and the ratio of Sn content to Ag content (Sn/Ag) is 0.5 〜 4. Further, in the negative electrode active material 2, impurities (copper, oxygen, and the like) from the negative electrode current collector which are inevitably mixed in the film formation are present, but in the present invention, the impurities are removed to calculate the C, Ag, and Sn contents. Therefore, the negative electrode active material 2 is composed of C, Sn, and Ag, and the content of C is 50 at% or more, and the total of the content of Sn and the content of Ag is less than 50 at%. [Amorphous carbon] The amorphous carbon has a sp2 and sp3 bond of carbon, and exhibits, for example, a crystal structure such as diamond carbon. The sp3 bond (carbon matrix) of carbon in the structure exhibits a function of suppressing the change in the volume of Sn dispersed in the amorphous carbon at the time of charge and discharge. Further, from the viewpoint of an increase in charge and discharge capacity, amorphous carbon is preferably a structure having lithium having a structure of absorbing graphite or the like. The content of the amorphous carbon in the negative electrode active material 2 is 50% by number or more. By dispersing Sn and Ag in amorphous carbon, it is possible to improve charge/discharge capacity, cycle characteristics, and high-rate charge and discharge characteristics, and in particular, by setting the content of amorphous carbon within the above range, even if it is repeated After charging and discharging, since the volume change of Sn can be alleviated by the carbon matrix, good cycle characteristics can be obtained. When the content of amorphous carbon is less than 50 at%, the volume change of Sii cannot be alleviated by the carbon matrix, and the cycle characteristics are deteriorated. It is preferably 55 at% or more, more preferably 60 at% or more. [Sn and Ag] Since Sn and Ag are metals which can be alloyed with lithium and have a low melting point, they are not alloyed with carbon having a high melting point and are dispersed in amorphous carbon. Further, the total of the content of Sri and the content of Ag is less than 50 at%, and the ratio is set to (Sn/Ag) of 0.5 to 4. By dispersing Sn and Ag in amorphous carbon of 50 at% or more of the negative electrode active material 2 (dispersed in a nano-cluster shape), and setting Sn/Ag to 0.5 to 4, the conventional negative electrode material is used. In comparison, it is possible to form a negative electrode material which is excellent in charge and discharge capacity and cycle characteristics and which can be charged and discharged at a high speed. By dispersing Sn and Ag in the amorphous carbon of the negative electrode active material 2, it is possible to improve the charge/discharge capacity and the high-rate charge and discharge characteristics. In particular, by setting Sn/Ag to 0.5 to 4, the charge can be further increased. Discharge capacity and high speed charge and discharge characteristics. Here, S η improves the charge and discharge capacity -12-201110446 by absorbing Li. Further, Ag improves the high-rate charge and discharge characteristics by increasing the diffusion rate of Li ions and the electron conductivity of the negative electrode active material 2. When the amount of Sn/Ag in the negative electrode active material 2 exceeds 4, the amount of Ag which is responsible for the diffusion of Li ions and the conduction of electrons is small with respect to Sn which is occluded by Li. Therefore, the effect of improving the charge and discharge rate is reduced. In addition, when Sn/Ag is less than 0.5, the ratio of Sn which is responsible for Li occlusion in the negative electrode active material 2 is reduced, so that the charge and discharge capacity is decreased. Here, the particle diameters of Sn and Ag dispersed in the amorphous carbon are preferably 0.5 to 100 nm. By dispersing the particle diameters of Sn and Ag in a nanocrystal cluster shape of 0.5 to 100 nm, the volume change of Sn and Ag at the time of charge and discharge can be further relaxed, and the charge/discharge capacity and the high-rate charge and discharge characteristics can be improved. The control of the particle diameters of S η and Ag is carried out by controlling the composition of the amorphous carbon and the metal (Sn and Ag) in the negative electrode active material 2. 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. Further, the measurement of the particle diameters of Sn and Ag can be carried out based on the semi-radius of the intensity of the ray of the metal observed by FIB-TEM observation or film X (Aix) ray diffraction. Further, the analysis of the composition of the negative electrode active material 2 can be carried out by the Auger electron spectrometer analysis (AES analysis), and the method for producing the negative electrode material for a lithium ion secondary battery according to the present invention. It is characterized in that Sn and Ag are dispersed in amorphous carbon of 50 at% or more, and the negative electrode active material 2 having a ratio of Sn/Ag of 0.5 to 4 is formed by vapor deposition at -13-201110446. On body 1. 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. After the negative electrode current collector 1 is formed by the negative electrode current collector forming step, the negative electrode active material forming step is characterized in that it is characterized by (The anode active material 2' having a dispersion of 311 and Å in the amorphous carbon of (^% or more) and having a ratio of 811/person 8 of 〇5 to 4 is formed on the anode current collector 1 by vapor deposition. In the following, the negative electrode current collector forming step is a step of forming the negative electrode current collector 1. In order to form the negative electrode active material 2, a negative electrode current collector is prepared. In the case of the negative electrode current collector 1, as described above, the known negative electrode current collector 1 may be used. Further, the negative electrode current collector forming step can correct the deformation of the negative electrode current collector 1 and [Rear and the like] [Negative electrode active material forming step] The negative electrode active material forming step is performed by dispersing S η and Ag in amorphous carbon of 50 at% or more by vapor deposition, and at the same time The fraction of Sn and Ag in crystalline carbon The formed negative electrode active material 2 is formed on the negative electrode current collector 1. By using a vapor phase deposition method, Sn and Ag are dispersed in a nanocrystalline cluster in an amorphous carbon of 50 at% or more. At the same time, the anode active material 2 can be formed on the anode current collector 1. In addition, the composition of the amorphous carbon and the metal (Sn and Ag) can be freely controlled in a wide range, and at the same time, it can be easily -14-201110446 By controlling the thickness of the film (negative electrode active material 2), the negative electrode active material 2 can be easily and easily formed on the negative electrode current collector 1. The thickness of the film is preferably 0.1 to 100/zm. Further, in the production method of the present invention By using a vapor deposition method, a film (negative electrode active material 2) obtained by dispersing Sri and Ag in amorphous carbon is formed on the negative electrode current collector 1 by vapor deposition to obtain a negative electrode material 10. Therefore, the step of applying the graphite carbon powder to the negative electrode current collector in the conventional production method, the step of drying the applied powder, and the application of the dried powder to the negative electrode current collector can be omitted. And the process of increasing the density. For the vapor deposition method, a chemical vapor deposition method (CVD: Chemical Vapor Deposition method) or a physical vapor deposition method (PVD: Physical Vapor Deposition method) may be used, and as a CVD method, there is a plasma CVD method as a PVD method having a vacuum. The vapor deposition method 'sputtering method, ion plating method, arc ion plating method (AIP), laser ablation method, etc. In particular, when a thick film is required, a method of using a film forming speed is required, and the AIP method is effective. For example, if the right side of the crucible is subjected to arc discharge as graphite, the graphite is evaporated as carbon atoms or ions by the heat of the arc discharge, and amorphous carbon can be deposited on the surface of the negative electrode current collector. Further, in the AIP method using a graphite target, in addition to carbon atoms or ions from the target surface generated by arc discharge, fine particles (macroscopic particles) of graphite from several to several tens of 111 are also emitted and are in the negative electrode. Since the current collector is deposited, it is possible to form a film having a large graphite structure as compared with the sputtering method or the ion plating method. Therefore, a film which occludes more lithium can be formed. When the amorphous carbon film is formed by the AIP method, if Sn and Ag are evaporated by vacuum evaporation or sputtering in the same chamber as in -15 - 201110446, Sn and Ag can be formed. Amorphous carbon film (negative electrode active material 2). In addition, when the discharge is performed by the AIP method, when a hydrocarbon gas such as methane or ethylene is introduced, the hydrocarbon gas is decomposed by arc discharge and deposited as an amorphous carbon film on the surface of the negative electrode current collector. The film formation speed is further increased. Next, an example of a method of producing a negative electrode material 10 for a lithium ion battery using a sputtering method and a case of using the AIP method will be described with reference to FIGS. 2 and 3, and any material used in the vapor deposition method will not be described. Limited to these materials. In addition, the configuration of the sputtering apparatus 20 and the AIP-sputtering composite apparatus 30 is not limited to those shown in FIGS. 2 and 3, and a known apparatus can be used, and a sputtering method can be used, as shown in FIG. First, in the chamber 21 of the sputtering apparatus 20, a carbon target 23 having a thickness of 5 mm and a tin target 22, and a silver target 24, and a substrate having a length of 50 x 50 Å and a thickness of 0.02 mm (copper foil) are provided. 25 is provided in such a manner as to align with the carbon target 23, the tin target 22, and the silver target 24. Then, the pressure in the chamber 21 is 1x1 (vacuum is set to be less than T3Pa, and the inside of the chamber 21 is in a vacuum state. Thereafter, Ar gas is introduced into the chamber 21 to change the pressure in the chamber 21 〇.26Pa, DC (direct current) is applied to each target to generate plasma, and the carbon target 23, the tin target 22, and the silver target 24 are sputtered, thereby forming a substrate (copper foil) as a negative electrode current collector. On the other hand, a film (negative electrode active material) in which tin and silver are dispersed in amorphous carbon is formed into a film, whereby a negative electrode material for a lithium ion secondary battery can be produced. For the case of using the AIP method, as shown in FIG. First, a graphite target 32 having a thickness of 16 mm and a graphite target 32 having a thickness of 16 mm and a diameter of 6 mm and a silver target 33 having a thickness of 6 mm are provided in the chamber 31 of the AIP--16-201110446 sputtering composite device 30, and the length 50x is 50 χ. A copper foil 35 having a thickness of 〇2 mm is provided on the surface of the revolving cylindrical substrate stage 36. Then, a vacuum is applied in such a manner that the pressure in the chamber 31 is 1 <10_3?& 31 is in a vacuum state. Thereafter, Ar gas is introduced into the chamber 31, so that the pressure in the chamber 31 becomes zero. At 26 Pa, DC (direct current) is applied to the graphite target 32, the tin target 34, and the silver target 33 to cause arc discharge of the graphite target 32, and glow discharge is generated by the silver target 33 and the tin target 34 to thermally evaporate graphite by arc discharge. And the tin and the silver are evaporated by the jet of the gas. Thereby, a film (negative electrode active material) in which tin and silver are dispersed in the amorphous carbon is formed on the copper foil 35 as the negative electrode current collector. Therefore, a negative electrode material for a lithium ion secondary battery can be produced. Further, each time the present invention is carried out, for example, a negative electrode current collector may be included between or before each of the above steps in a range that does not adversely affect the respective steps. The lithium ion battery of the present invention is a battery using the negative electrode material for a lithium ion battery described above, and can be manufactured by using the negative electrode material of the present invention. A lithium ion battery with high charge and discharge capacity, good cycle characteristics, and excellent high-speed charge and discharge characteristics. "Formation of Lithium Ion Battery" . 201110446 Examples of the form of the lithium ion secondary battery include a cylindrical type, a coin type, a substrate-mounted film type, an angle type, a sheet type, and the like, and various types of lithium ion batteries can be used as long as the negative electrode material of the present invention can be used. A material, a positive electrode material, an electrolyte which insulates the electrode material, and an electrolyte which moves the electric charge between the auxiliary electrode materials, and a battery case which accommodates these. Hereinafter, each structure will be described. <Anode material> Use of a negative electrode material In the above negative electrode material of the present invention, the negative electrode material is produced by the production method of the above invention. <Positive Electrode Material> The positive electrode material is not particularly limited, and a known material such as a lithium-containing oxide such as LiCoO 2 , UNi 02 or LiMn 204 can be used. The method for producing the positive electrode material is not particularly limited, and a known method may be employed. For example, a binder is added to the powdery positive electrode materials, 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 aluminum foil. <Isolation material> The separator is not particularly limited, and a known material such as a sheet of a porous body such as polyethylene or polypropylene or a separator such as a non-woven fabric can be used.
-18- 201110446 <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 生成的鋰離子的移動。 作爲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 混合多種溶劑使用，該溶劑爲：碳酸伸乙酯、碳酸伸丙酯 、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、乙睛、丙腈、 四氫呋喃、7-丁內酯、2-甲基四氫呋喃、1，3-二氧雜戊環 、4-甲基-1，3-二氧雜戊環、1，2-二甲氧基乙烷、1,2-二乙 氧基乙烷、二乙基醚、環丁颯、甲基環丁碾、硝基甲烷、 N，N-二甲基甲醯胺、二甲基亞颯等溶劑。 作爲用作電解液的電解質而使用的鋰鹽，可以使用例 如 LiC104 、 LiAsF6 、 LiPF6 、 LiBF4 、 LiB(C6H5)4 ' LiCl 、 CH3S03Li、CF3S03Li等，可以單獨使用這些鹽或可以多種 混合使用。 <電池盒> 電池盒收容前述的負極材料、正極材料、隔離材料、 電解液等。 另外，在製造鋰固體蓄電池、聚合鋰蓄電池的情況下 ，藉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。 -19- 201110446 [實施例] 接著，針對本發明的鋰離子蓄電池用負極材料、及其 製造方法、以及鋰離子蓄電池，具體地說明比較滿足本發 明之要件的實施例和不滿足本發明要件之的比較例。 [第1實施例] 在如第2圖所示的濺射裝置的腔室內設置p 10 Ommx厚 度5mm的碳靶、錫靶及銀靶（FuruChi化學股份有限公司） 。另外，將長50x寬50x厚度0.02mm的銅箔（Furuchi化學 股份有限公司）按照對向於碳靶、錫靶、及銀靶的方式進 行設置，接著，按照腔室內的壓力爲lxl 0·3 Pa以下的方式 抽成真空，使腔室內處於真空狀態。其後，向腔室內導入 Ar氣體，使腔室內的壓力變爲〇.26Pa，對各靶材施加DC ( 直流）而產生等離子，濺射碳靶、錫靶、及銀靶。藉由調 整施加於各靶材的電流，在銅箔（負極集電體）上將錫及 銀分散於非晶質碳中的膜（負極活性物質）予以成膜，而 製造鋰離子蓄電池用負極材料。 膜（負極活性物質）的Ag、Sn及C含量係藉由歐傑電 子譜儀分析（AES分析）算出。在此，AES分析中使用 Perkinelmer社製PH 1 65 0掃描型歐傑電子譜儀，針對直徑10 //m的區域進行分析。在膜（負極活性物質）中存在10 at % 以下的成膜時不可避免地混入的來自銅箔的銅及氧等雜質 ’將它們去除，以算出膜（負極活性物質）中的Ag、Sn、 C含量。 -20- 201110446 針對這樣製造的負極材料（試料No.1〜8)，藉由以 下的方法進行充放電特性評價。 [充放電特性評價] 配置得到的負極材料和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。 作爲電解液，使用將lmol/1的6氟化磷酸鋰鹽以體積比1對1 溶解在碳酸伸乙酯和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價用電池單元。另外，第4 圖顯示使用的評價用電池單元的構造的示意圖。 針對該評價用電池單元，在室溫下，進行將截止電壓 充電時設爲〇.IV、放電時設爲1.0V作爲一循環的充放電試 驗。充放電試驗藉由恆定電流進行。 測定充放電時電流設定爲1C速率、及10C速率時的初 期放電容量。另外，在10C速率下進行100循環的充放電試 驗，並測定此時的容量維持率。在此，容量維持率藉由“ 100循環後的放電容量+初期放電容量χίοο”算出。 1C速率下的初期放電容量（初期容量）爲超過 5 60mAh/g(以往的石墨負極材料理論容量的約1.5倍）的 情況下，充放電容量良好° 另外，在10C速率下的初期放電容量（初期容量）在 超過1C速率下的初期放電容量的80 %的情況下，高速充放 電特性良好（即，充放電速度快）。 進而，將10C速率下的100循環的充放電試驗後的容量 C S1 -21 - 201110446 維持率爲80 %以上者設定爲循環特性良好。 這些結果如表1所示。另外，第5圖顯示膜中的非晶質 碳的含量與10C速率下100循環的充放電試驗後的容量維持 率的關係。另外，第6圖顯示膜中的Sii / Ag與10C初期容 量相對於1 C初期容量的比例（1 0C / 1 C )之間的關係，及 S n/ Ag與1C初期容量之間的關係。 [表1] 試料 No. 1C放電時 10C放電時 膜組成（at%) 初期容量 初期容量 10C/1C 100循環後的容 Sn Ag C Sn/Ag (mAh/g) (mAh/g) (%) 量維持率（％) 1 32 9 59 3.56 640 560 88 89 2 25 22 53 1.14 620 570 92 82 3 20 20 60 1 600 530 88 93 4 13 25 62 0.52 580 510 88 92 5 31 35 34 0.89 610 560 92 30 6 32 7 61 4.57 610 430 70 84 7 33 0 67 一 640 420 66 96 8 0 26 74 0 260 220 85 92 (注）10C/1C: 10C初期容量相對於1C初期容量的比例 如表1所示’由於作爲實施例的試料No.1〜4滿足本發 明的要件’因此可以發揮充分的充放電特性（充放電容量 、高速充放電特性及循環特性）。 另一方面’膜中的C含量不滿足本發明的要件的比較 例（試料No.5)不能充分發揮循環特性。另外，在膜中的 Sn/Ag不滿足本發明的要件的比較例（試料ν〇·6)、膜中 -22- 201110446 不包含Ag的比較例（試料No. 7 )，不能發揮充分的高速充 放電特性。另外’在膜中不包含Sn的比較例（試料Νο·8) 不能發揮充分的充放電容量。 另外，在作爲實施例的試料No.l〜4中，用FIB-TEM 觀察時，分散於膜（負極活性物質）的非晶質碳中的Sn及 Ag的粒徑爲2〜5nm，用SEM觀察時，膜的厚度爲0.45〜 0 · 5 5 # m。 [第2實施例] 在第2實施例中，作爲成膜方法，係藉由以AIP法將非 晶質碳成膜，並以濺射法將Sn和Ag同時成膜而製造鋰離子 電池用負極材料。 在如圖3所示的AIP -濺射複合裝置的腔室內，設置 plOOmmx厚度16mm的石墨祀、少6英寸X厚度6mm的錫耙 及銀靶（？111*11(；11丨化學股份有限公司），並將長5(^寬5 0><厚 度0.02mm的銅箔（Furuchi化學股份有限公司）設置在公 轉的圓筒狀的基板台表面，按照腔室內的壓力爲lxl(T3Pa 以下的方式抽成真空，使腔室內處於真空狀態。其後，向 腔室內導入Ar氣體，使腔室內的壓力變爲0.26Pa，對石墨 靶、錫靶、及銀靶施加DC (直流），而使石墨靶產生電弧 放電，使錫靶及銀靶產生輝光放電，使石墨藉由電弧放電 的熱蒸發，並且使錫及銀藉由氬的濺射蒸發。藉此，在銅 箔（負極集電體·）上將在非晶質碳中分散錫及銀而成的膜· (負極活性物質）予以成膜，而製造鋰離子蓄電池用負極 -23- 201110446 材料。此時的電弧放電電流爲60A、濺射功率爲500W，施 加於銅箔（基板）的偏壓爲0V，進行1小時的成膜。 針對該負極材料中的非晶質碳中的錫及銀的分散狀態 ，藉由FIB-TEM觀察進行調查，碳爲在非晶質構造中含有 亂層構造之石墨的構造，在碳相中，對分散有粒徑5〜 10nm的錫粒子及銀粒子的構造進行觀察。另外，以SEM對 截面進行觀察，膜（負極活性物質）的膜厚爲5ym。另外 ，C、Sn及Ag組成的分析與第1實施例相同，實施歐傑電 子譜儀分析（AES分析），得到C爲88at%、Sn爲4at%、Ag 爲 8 a t %。 針對這樣製造的試料，藉由與第1實施例相同的方法 ，進行充放電特性評價。其結果，在1 C速率下的初期放電 容量爲5 8 0mAh/g，在10C速率下充放電的情況下的初期放 電容量爲530 mAh/g，在10C速率下100循環後的容量維持 率爲96%。這樣，即使以AIP法將非晶質碳成膜，以濺射 法將Sn及Ag同時成膜而得到的負極材料，亦顯示優良的充 放電特性（充放電容量 '高速充放電特性及循環特性）。 從以上的結果可知，根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 性和高速充放電特性的鋰離子蓄電池。 以上針對本發明的最佳的實施形態、實施例進行了說 明，但本發明不限定於前述實施形態、實施例，可以在適 合於本發明宗旨的範圍內廣泛地變更並改變而予以實施， 這些均包含在本發明的技術範圍內。 -24- 201110446 極 負 用 池 電 蓄 子 0 mc 鋰 的 明 發 本 示 顯 地 性 _意 明示 說请 單圖 簡 1 式[II 圖 材料之構成的剖面圖； [第2圖]爲用於製造本發明的鋰離子蓄電池用負極材料 之濺射裝置的示意圖； [第3圖]爲用於製造本發明的鋰離子蓄電池用負極材料 之AIP-灑射複合裝置的示意圖； [第4圖]爲顯示在實施例中使用的評價用電池單元之構 造的示意圖； [第5圖]爲顯示在實施例中，負極活性物質中的非晶質 碳的含有率和在10C速率下進行100循環後的容量維持率之 關係的曲線圖； [第6圖]爲顯示在實施例中，負極活性物質中的Sn/Ag 與1 0 C初期容量相對於1 C初期容量的比例（1 〇 c /1 C )之間 的關係、及Sn/Ag與1 C初期容量的關係的曲線圖。 【主要元件符號說明】 1 :負極集電體 2 :負極活性物質 鋰離子蓄電池用負極材料（負極材料） -25--18- 201110446 <Electrolyte> The electrolyte is injected into the battery case and sealed. When the electrolyte is charged and discharged, the movement of lithium ions generated by the electrochemical reaction between the negative electrode material and the positive electrode material can be performed. As the solvent for the electrolyte of the electrolytic solution, a known aprotic or low dielectric constant solvent capable of dissolving the lithium salt can be used. For example, it may be used singly or in combination with a plurality of solvents: ethyl carbonate, propyl carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, tetrahydrofuran, 7-butyl Lactone, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-dimethoxyethane, 1,2-di Solvents such as ethoxyethane, diethyl ether, cyclobutyl hydrazine, methylcyclobutyl milling, nitromethane, N,N-dimethylformamide, dimethyl alum. As the lithium salt used as the electrolyte for the electrolytic solution, for example, LiC104, LiAsF6, LiPF6, LiBF4, LiB(C6H5)4'LiCl, CH3S03Li, CF3S03Li or the like can be used, and these salts can be used singly or in combination of plural kinds. <Battery Case> The battery case houses the above-described negative electrode material, positive electrode material, separator, electrolyte solution, and the like. In addition, when a lithium solid secondary battery or a lithium ion secondary battery is produced, the negative electrode material for a lithium ion secondary battery of the present invention can be used together with a known positive electrode material, a polymer electrolyte, or a solid electrolyte, thereby producing a high safety and high capacity. Battery. -19-201110446 [Embodiment] Next, the 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 specifically described as an embodiment satisfying the requirements of the present invention and not satisfying the requirements of the present invention. Comparative example. [First embodiment] A carbon target having a p 10 Ommx thickness of 5 mm, a tin target, and a silver target (Furu Chi Chemical Co., Ltd.) were placed in a chamber of a sputtering apparatus as shown in Fig. 2 . In addition, a copper foil (Furuchi Chemical Co., Ltd.) having a length of 50x, a width of 50x and a thickness of 0.02 mm is disposed in such a manner as to face a carbon target, a tin target, and a silver target, and then, according to the pressure in the chamber, lxl 0·3 The following method of Pa is evacuated to bring the chamber to a vacuum. Thereafter, Ar gas was introduced into the chamber, and the pressure in the chamber was changed to 2626 Pa. DC (DC) was applied to each target to generate plasma, and a carbon target, a tin target, and a silver target were sputtered. By adjusting the current applied to each target, a film (negative electrode active material) in which tin and silver are dispersed in amorphous carbon on a copper foil (negative electrode collector) is formed to form a negative electrode for a lithium ion secondary battery. material. The Ag, Sn, and C contents of the film (negative electrode active material) were calculated by Oujie electron spectrometer analysis (AES analysis). Here, in the AES analysis, a PH 1 65 0 scanning type Auger electron spectrometer manufactured by Perkinelmer Co., Ltd. was used for analysis of a region having a diameter of 10 // m. In the film (negative electrode active material), impurities such as copper and oxygen which are inevitably mixed in the film formation at the time of film formation (negative electrode active material) are removed, and Ag and Sn in the film (negative electrode active material) are calculated. C content. -20-201110446 The negative electrode materials (samples Nos. 1 to 8) thus produced were evaluated for charge and discharge characteristics by the following method. [Evaluation of Charging and Discharging Characteristics] The obtained negative electrode material and metal lithium which is a counter electrode as a positive electrode material were sandwiched between a two-electrode material and a separator made of a porous material made of polypropylene. As the electrolytic solution, a solution of dissolving 1 mol/l of lithium hexafluoride phosphate in a volume ratio of 1 to 1 in a mixed organic solvent of ethyl carbonate and dimethyl carbonate was used to produce a two-pole battery cell. Battery unit for evaluation. In addition, FIG. 4 is a schematic view showing the structure of the evaluation battery unit used. For the battery cell for evaluation, a charge-discharge test was performed at room temperature to set 〇.IV when the off-voltage was charged and 1.0 V as the discharge. The charge and discharge test was carried out by a constant current. The current at the time of charge and discharge was measured as the initial discharge capacity at the 1 C rate and at the 10 C rate. Further, a charge and discharge test of 100 cycles was performed at a rate of 10 C, and the capacity retention rate at this time was measured. Here, the capacity retention rate is calculated by "discharge capacity after 100 cycles + initial discharge capacity χίοο". When the initial discharge capacity (initial capacity) at the 1C rate is more than 5 60 mAh/g (about 1.5 times the theoretical capacity of the conventional graphite negative electrode material), the charge/discharge capacity is good. In addition, the initial discharge capacity at the 10 C rate ( When the initial capacity is 80% of the initial discharge capacity at a rate higher than 1 C, the high-rate charge and discharge characteristics are good (that is, the charge and discharge speed is fast). Further, the capacity C S1 -21 - 201110446 after the 100-cycle charge and discharge test at the 10C rate was maintained at a rate of 80% or more, and the cycle characteristics were good. These results are shown in Table 1. Further, Fig. 5 shows the relationship between the content of amorphous carbon in the film and the capacity retention rate after a charge and discharge test of 100 cycles at a rate of 10 C. Further, Fig. 6 shows the relationship between the ratio of Sii / Ag and the initial capacity of 10C to the initial capacity of 1 C (1 0C / 1 C ) in the film, and the relationship between S n / Ag and the initial capacity of 1C. [Table 1] Sample No. 1C Discharge at 10C discharge film composition (at%) Initial capacity Initial capacity 10C/1C Capacity after Sn cycle Ag Ag C Sn/Ag (mAh/g) (mAh/g) (%) Capacity maintenance rate (%) 1 32 9 59 3.56 640 560 88 89 2 25 22 53 1.14 620 570 92 82 3 20 20 60 1 600 530 88 93 4 13 25 62 0.52 580 510 88 92 5 31 35 34 0.89 610 560 92 30 6 32 7 61 4.57 610 430 70 84 7 33 0 67 A 640 420 66 96 8 0 26 74 0 260 220 85 92 (Note) 10C/1C: The ratio of the initial capacity of 10C to the initial capacity of 1C is shown in Table 1. In the sample Nos. 1 to 4 which are examples, the requirements of the present invention are satisfied. Therefore, sufficient charge and discharge characteristics (charge and discharge capacity, high-rate charge and discharge characteristics, and cycle characteristics) can be exhibited. On the other hand, the comparative example (sample No. 5) in which the C content in the film did not satisfy the requirements of the present invention could not sufficiently exhibit the cycle characteristics. In addition, the comparative example (sample ν〇·6) in which the Sn/Ag in the film does not satisfy the requirements of the present invention, and the comparative example (sample No. 7) in which the film -22-201110446 does not contain Ag cannot exhibit sufficient high speed. Charge and discharge characteristics. Further, the comparative example (sample Νο·8) which does not contain Sn in the film does not exhibit sufficient charge and discharge capacity. In addition, in the samples No. 1 to 4 which are examples, the particle diameters of Sn and Ag dispersed in the amorphous carbon of the film (negative electrode active material) are 2 to 5 nm when observed by FIB-TEM, and SEM is used. When observed, the thickness of the film was 0.45 to 0 · 5 5 # m. [Second Embodiment] In the second embodiment, as a film formation method, amorphous carbon is formed into a film by the AIP method, and Sn and Ag are simultaneously formed by sputtering to produce a lithium ion battery. Anode material. In the chamber of the AIP-sputtering composite device shown in FIG. 3, a graphite crucible having a thickness of 16 mm of plOOmmx and a tin crucible and a silver target having a thickness of 6 mm and a thickness of 6 mm are provided (?111*11 (;11丨Chemical Co., Ltd.) ), a copper foil (Furuchi Chemical Co., Ltd.) having a length of 5 (5 ft. 0>lt; 0.02 mm) is placed on the surface of a revolving cylindrical substrate table, and the pressure in the chamber is lxl (T3Pa or less). The method is evacuated to bring the chamber into a vacuum state. Thereafter, Ar gas is introduced into the chamber to change the pressure in the chamber to 0.26 Pa, and DC (direct current) is applied to the graphite target, the tin target, and the silver target. The graphite target generates an arc discharge, causes a glow discharge of the tin target and the silver target, causes the graphite to evaporate by thermal arc discharge, and causes tin and silver to be evaporated by sputtering of argon. Thereby, the copper foil (negative current collector) -) A film (negative electrode active material) in which tin and silver are dispersed in amorphous carbon is formed into a film to produce a negative electrode for a lithium ion battery, -23-201110446. The arc discharge current at this time is 60 A. The sputtering power is 500W, and the bias applied to the copper foil (substrate) The film was formed at a pressure of 0 V for 1 hour. The dispersion state of tin and silver in the amorphous carbon in the negative electrode material was investigated by FIB-TEM observation, and carbon contained a disorder layer in the amorphous structure. The structure of the graphite of the structure was observed in the carbon phase, and the structure of the tin particles and the silver particles having a particle diameter of 5 to 10 nm was observed. The cross section of the film (the negative electrode active material) was observed to be 5 μm. In addition, the analysis of the compositions of C, Sn, and Ag was carried out in the same manner as in the first example, and the analysis of Auger electron spectrometer (AES analysis) was carried out to obtain Cat of 88 at%, Sn of 4 at%, and Ag of 8 at %. The sample was evaluated for the charge and discharge characteristics by the same method as in the first example. As a result, the initial discharge capacity at the 1 C rate was 580 mAh/g, and the initial charge at the 10C rate was charged and discharged. The discharge capacity was 530 mAh/g, and the capacity retention rate after 100 cycles at 10 C rate was 96%. Thus, even if amorphous carbon was formed by the AIP method, Sn and Ag were simultaneously formed by sputtering. Anode material also shows excellent charge and discharge characteristics (charge and discharge capacity) 'High-speed charge and discharge characteristics and cycle characteristics. From the above results, it is understood that the lithium ion battery for lithium ion battery according to the present invention can obtain a lithium ion battery having sufficient charge and discharge capacity, excellent cycle characteristics, and high-rate charge and discharge characteristics. 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 can be widely modified and changed within the scope of the gist of the present invention. These are all included in the technical scope of the present invention. -24- 201110446 Extremely negative pool electric charge 0 mc Lithium of the Ming Dynasty shows the obviousness _ meaning that the single figure is simple 1 type [II composition of the material [Fig. 2] is a schematic view of a sputtering apparatus for producing a negative electrode material for a lithium ion secondary battery of the present invention; [Fig. 3] is an AIP-sprinkling for producing a negative electrode material for a lithium ion secondary battery of the present invention. Schematic diagram of the radiation composite device; [Fig. 4] is a schematic view showing the configuration of the evaluation battery unit used in the embodiment; [Fig. 5] is shown in the implementation In the example, the relationship between the content ratio of amorphous carbon in the negative electrode active material and the capacity retention rate after 100 cycles at a rate of 10 C; [Fig. 6] is shown in the examples, in the negative electrode active material. A graph showing the relationship between Sn/Ag and the ratio of initial capacity of 10 C to the initial capacity of 1 C (1 〇c /1 C ), and the relationship between Sn/Ag and initial capacity of 1 C. [Explanation of main component symbols] 1 : Negative current collector 2 : Negative electrode active material Negative electrode material for lithium ion battery (negative electrode material) -25-