TWI258883B - Composite particle and negative electrode material using the same, negative electrode and lithium ion secondary battery - Google Patents

Composite particle and negative electrode material using the same, negative electrode and lithium ion secondary battery Download PDF

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TWI258883B
TWI258883B TW093129041A TW93129041A TWI258883B TW I258883 B TWI258883 B TW I258883B TW 093129041 A TW093129041 A TW 093129041A TW 93129041 A TW93129041 A TW 93129041A TW I258883 B TWI258883 B TW I258883B
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metal
negative electrode
graphite
composite particle
composite particles
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TW093129041A
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TW200514296A (en
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Yasushi Madokoro
Kunihiko Eguchi
Katsuhiro Nagayama
Toshihide Suzuki
Tatsuya Nobusawa
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Jfe Chemical Corp
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Priority claimed from JP2004053793A external-priority patent/JP3957692B2/en
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to composite particles comprising a metal alloyable with lithium and a graphite material and carbon material, wherein at least portion of the metal is in contact with at least one material selected from the group consisting of graphite materials and carbon materials and wherein the ratio of void around the metal to total void is 20% or more. There are further provided, utilizing the composite particles, a negative electrode material for lithium ion secondary battery, negative electrode and lithium ion secondary battery. When these composite particles are used in a negative electrode material for lithium ion secondary battery, there can be accomplished three characteristics of large discharge capacity, excellent cycle performance and excellent initial charge discharge efficiency among the properties of lithium ion secondary battery.

Description

1258883 九、發明說明： 【發明所屬之技術領域】 本發明係關於將可與鋰合金化之金屬與石墨材料及 碳材料複合化之複合粒子，以及使用其之鋰離子二次 之負、極材料、負極暨鋰離子二次電池。 【先前技術】 相較於其他二次電池，鋰離子二次電池具有高電壓 能量密度，因此廣泛普及為電子機器之電源。近年來 子機器之小型化或高性能化急速進展，進一步提高鋰 二次電池之能量密度的期望日漸增高。 目前，裡離子二次電池一般係於正極使用L i C 〇 0 2、 極使用石墨。然而，石墨負極之充放電的可逆性優異 放電容量已達到接近相當於層間化合物（L i C 6 )之理 (3 7 2 mAh/g )的數值。因此，為了進一步提高電池之 密度，必須開發放電容量較石墨大的負極材料。 金屬鋰具有作為負極材料最大的放電容量。然而， 電時，鋰會以樹突狀析出而使負極劣化，因此具有電 充放電循環變短的問題。又，亦有樹突狀析出的鋰貫 隔片而到達正極，造成電池短路的可能性。 因此，作為代替金屬鋰之負極材料，與鋰形成合金 屬或金屬化合物已被檢討。此等合金負極之放電容量 屬鋰小，但遠遠超越於石墨。然而，因伴隨著合金化 積膨脹，發生活性物質的粉末化*剝離5鋰離子二次 之循環特性並未達到實用程度。 312XP/發明說明書(補件)/93-12/93129041 /或 電池 、南 ，電 離子 於負 ，其 論值 能量 於充 池的 通分 之金 較金 的體 電池 1258883 為解決如上所述之合金負極之缺點，金屬或金屬化合物 與石墨材料及/或碳材料之複合化而成之負極的開發正被 檢討中。 為了吸收伴隨合金化所產生的膨脹，使複合材料内存在 孔隙係有效的方法。然而，若孔隙過多，會導致複合材料 之強度或導電性降低。亦即，複合材料之孔隙量相對於材 料本身之耐破壞性與導電性係二律背反（a n t i η 〇 m y )之關 係，欲使兩者平衡並完美符合要求極為困難。 例如，於日本專利第3 3 6 9 5 8 9號公報中，揭示將可與鋰 等鹼金屬形成合金之金屬物質、石墨材料及碳材料所構成 之複合材料使用作為電極材料。於此複合材料中，該碳材 料擔任結合或被覆金屬物質與石墨材料之角色。以利用氬 雷射之拉曼（R a m a η )分光法所測定之該碳材料表面的D 帶域1 3 6 0 c ηΤ 1波峰強度I D與G帶域1 5 8 0 c πΓ 1波峰強度I G 之比I D / I G ( R值）顯示為0 · 4以上。其顯示該碳材料並未 被石墨化。然而，於此複合材料之情況，碳材料亦滲透至 複合材料之内部，因此無法避免該金屬物質與鋰合金化時 之體積膨脹對複合材料的破壞，仍會導致循環特性之降低。 另一方面，於日本專利特開2 0 0 0 - 1 7 3 6 1 2號公報中，揭 示一種於含矽粒子之表面的一部分或整面固定纖維狀碳之 負極材料。此技術之目的在於，即使放電時矽粒子收縮， 仍可藉由纖維狀碳來確保矽粒子間之導電性。然而，於此 構造中5雖可維持導電性5但卻無法吸收充電時所產生之 金屬膨脹，導致循環特性之降低。 6 312ΧΡ/發明說明書(補件)/93-12/93129041 1258883 日本專利第3 4 6 6 5 7 6號公報中，揭示一種由 含碳粒子所構成之以碳被覆多孔性粒子之負極 外，該含碳粒子相當於一種石墨材料。於該技勒 雖積極地使負極材料多孔質化，但仍因矽與鋰 體積膨脹而發生負極材料之構造破壞，依舊無 人滿足的循環特性。此外，由於含碳粒子（石 小至1 // m以下，容易發生電解液之分解反應， 電效率亦降低。 如上所述，於習知技術中，難以兼顧膨脹之 性之維持。 有鑑於上述之技術背景，本發明提供一種鋰 池，其於將含有可與鋰合金化之金屬、石墨材 料等3成分之複合粒子使用於鋰離子二次電池 時，可達成放電容量大、優異之循環特性以及 充放電效率。換言之，本發明之目的在於提供 子二次電池之該3性能之新穎複合粒子，以及 離子二次電池之負極材料、負極暨經離子二次 【發明内容】 本發明係關於一種複合粒子，其係將可與鋰 屬的至少一部分與選自石墨及碳材料所組成群 材料接觸，且該金屬周圍之孔隙相對於總孔隙 以上之含有該金屬、該石墨材料及該碳材料之 另外，此複合粒子較佳情況為，該石墨材料係 石墨及纖維狀石墨所組成群組之至少1材料。 312XP/發明說明書(補件)/93-12/93129041 含發粒子與 材料。另 -之例子中， 合金化時之 法得到可令 墨材料）縮 因此初期放 吸收與導電 離子二次電 料以及碳材 之負極材料 優異之初期 可滿足鋰離 使用其之經 電池。 合金化之金 組之至少1 為 2 0 v ο 1 % 複合粒子。 選自鱗片狀 7 1258883 又，此等複合粒子中，當該石墨材料為鱗片狀時，拉曼 光譜之D帶域之波峰強度對於G帶域之波峰強度之比以未 滿0 . 4為佳。 又，此等複合粒子中，該石墨材料為由X射線繞射所得 之平均晶格面間隔d 〇 〇 2在0 . 3 4 n m以下之纖維狀石墨為佳。 此外，上述之任一複合粒子中，該金屬之至少一部分接 觸於纖維狀石墨，且該等之至少外表面之一部分係以碳材 料被覆為佳。另外，此複合粒子進一步含有鱗片狀石墨更 佳。 又，上述之任一複合粒子中，該金屬以石夕為佳。 此外，上述之任一複合粒子中，該金屬之平均粒徑以 0.01 〜10// m 為佳。 又，上述之任一複合粒子中，該金屬以非晶質為佳。 此外，上述之任一複合粒子中，該複合粒子之比表面積 以2 0m2/g以下為佳。 又，上述之任一複合粒子中，該複合粒子之平均粒徑以 1〜5 0 // m為佳。 此外，於本案中，提供含有上述之任一複合粒子之鋰離 子二次電池用負極材料。又，亦提供使用該鋰離子二次電 池用負極材料之鋰離子二次電池用負極。此外，亦提供使 用該鋰離子二次電池用負極之鋰離子二次電池。 又，於本案中，亦提供一種複合粒子之發明，係於石墨 材質材料透過碳材質材料而與可和鋰合金化之金屬一體化 之複合粒子中，其特徵為，該複合粒子具有孔隙，且金屬 8 3 12XP/發明說明書(補件)/93- ] 2/93129041 1258883 周邊之孔隙相對於該複合粒子之總孔隙之比例為2 Ο %以 上。 【實施方式】 以下，更具體地說明本發明。 如上所述，習知之金屬-石墨（碳）型之複合材料中，無 法避免負極中之金屬與鋰形成合金時之膨脹所造成的循環 特性之降低。因此，本發明人等在保持負極之導電性之前 提下，同時研究可吸收該膨脹之構造的負極。結果發現， 僅增加複合粒子之總孔隙無法維持負極之導電性，但若於 構成金屬之周圍形成可吸收該膨脹之孔隙，則可在維持負 極導電性之同時防止複合粒子之粉末化或剝離，因而完成 本發明。 (複合粒子） 本發明之複合粒子係由可與鋰合金化之金屬之至少一部 分與選自石墨材料及碳材料所組成群組之至少1材料接 觸，且該金屬周圍之孔隙相對於總孔隙為2 Ο ν ο 1 %以上之 含有該金屬、該石墨材料及該碳材料之複合粒子。 該複合粒子中，係由該金屬之至少一部分與石墨材料或 碳材料亦或石墨材料及碳材料兩者接觸’且該金屬之周圍 之孔隙亦與該金屬表面之至少一部分接觸而構成。通常， 該複合粒子將多個該金屬粒子予以分散包覆，並分散而含 有多個不特定大小的孔隙。 本發明中，該金屬周圍之孔隙（以下亦稱為周圍孔隙） 對於複合粒子之總孔隙之比例必須為2 Ο ν ο 1 %以上。若未 9 312ΧΡ/發明說明書(補件)/93-12/93129〇41 1258883 滿2 Ο ν ο 1 % ，則無法吸收該金屬與鋰形成合金時之膨脹。 較佳的周圍孔隙度為4 Ο ν ο 1 %以上，更佳的周圍孔隙度為 5 Ο ν ο 1 %以上。另外，理論上來說，金屬的周圍孔隙度之上 限可能為1 0 0 % 。此時，係呈現複合粒子中之孔隙全部與 該金屬部分接觸之狀態。本案並不排除此種情形。然而， 通常，本發明之複合粒子中，周圍孔隙度之較適合上限值 可謂80〜90vol% 。 又，本發明之複合粒子中，總孔隙佔總體積之比例以 3〜50vol%為佳。其原因為，通常，若為3vol%以上，可 充分吸收因合金化所產生之體積膨脹，若為5 0 ν ο 1 %以下 則可充分保持複合粒子之強度。以3 0〜5 0 ν ο 1 %為特佳。 本發明之複合粒子之總孔隙之容積（c a p a c i t y )，例如可 將經粉碎並露出剖面之複合粒子以水銀孔隙度儀測定而得 到。又，自其可計算複合粒子整體之孔隙度（容積率）。 本發明中，金屬周圍之孔隙相對於複合粒子整體之總孔 隙的比例，可以以下方法求得。利用掃瞄式電子顯微鏡， 任意選定5 0個複合粒子，以4 0 0倍之倍率拍攝剖面照片。 自此剖面照片求得每個複合粒子之總孔隙面積的總計值與 每個金屬之周圍孔隙之總計值。利用此等複合粒子的 50 個值，求出金屬周圍孔隙面積相對於總孔隙面積之比例（面 積率），再算術平均為每個複合粒子，將此值作為本發明之 金屬的周圍孔隙度。由此剖面照片，可判斷該金屬之至少 一部分是否接觸於石墨材料及/或碳材料。 另外，複合粒子之質量組成係針對金屬，將複合粒子灰 10 312XP/發明說明書(補件)/93-12/93129041 1258883 化後，以發光分光法進行元素分析，取換算為金屬之濃度 的值。 石墨材料與碳材料係使用偏光顯微鏡，將複合粒子之剖 面放大為1 0 0 0倍並照相，著眼於任意1 0個複合粒子，自 由結晶性之高低所造成的外觀差異來判斷。又，兩者之比 例係粒子内部之石墨材料與碳材料所佔面積之比例之平均 值。 另外，石墨材料與碳材料所佔之面積比例，可製作複合 粒子之剖面的薄片並使用穿透式電子顯微鏡來觀察而求 出。此處，雖係求取石墨材料與碳材料之面積比例，由於 石墨材料與碳材料之密度並無太大差異，因此，於本發明 中，以上述方式求出之面積比例與質量比例幾乎相同。 由於本發明之複合粒子中於上述金屬之周圍存在有上述 孔隙，因此可改良鋰離子二次電池之循環特性。其原因在 於，充電時該金屬之膨脹被該孔隙吸收，可抑制含有該複 合粒子之負極材料的構造破壞。亦即，即便於金屬本身會 粉末化之情況，該負極材料整體的複合粒子之形態仍得以 維持，因此各複合粒子間的接觸得以保持，不會損害集電 性。故而推測其可抑制循環特性之降低。 本發明之複合粒子中，構成其之石墨材料以鱗片狀或纖 維狀為佳。 若該石墨材料為鱗片狀，則容易於複合粒子内形成孔 隙，尤其可提升循環特性等。另外，本發明之複合粒子中， 當該石墨材料為鱗片狀時，該複合粒子於拉曼光譜之D帶 11 312XP/發明說明書(補件)/93-12/93129041 1258883 域波峰強度（ID )相對於 G帶域的波峰強度（IG )之比 (ID/IG)以未滿0.4為佳。若使用波長514.5nm之氬雷射 測定複合粒子之拉曼光譜，可藉由D帶域之波峰強度（I D ) 相對於G帶域之波峰強度（I G )之比（I D / I G )來判定複合 粒子外表面的結晶性。該I D / I G比通常稱為「R值」，而本 發明之複合粒子以R值未滿0. 4者為佳。另外，通常G帶 域係於1 5 8 0 c ηΤ 1處、D帶域係於1 3 6 0 c πΓ 1處觀測，根據測 定誤差可分別於± 2 0 c πΓ 1之區域觀測。經由滿足上述複合粒 子之構造，可得到R值未滿0 . 4之複合粒子。此種複合粒 子之表面結晶性高，循環特性與初期充放電效率等優異， 因此特佳。另外，R值之較佳範圍為0 . 1 5〜0 . 3 8，更佳範圍 為 0· 2 〜0. 3。 另外，R值顯示0 . 4以上之情況為例如於石墨材料中使 用鱗片狀石墨以外之石墨材料，使石墨邊緣面露出於外表 面之情況。 另一方面，若該石墨材料為纖維狀，則可提升複合粒子 内之導電性，尤其可提升循環特性等。另外，本發明之複 合粒子中，該石墨材料為纖維狀時，該纖維狀石墨之X射 線折射之平均晶格面間隔d。ϋ 2在0 . 3 4 n m以下為佳。此種纖 維狀石墨之結晶性高，放電容量大，因此特佳。另外，晶 格面間隔之測定係使用 C u Κ α射線為X射線源、高純度矽 為標準物質，測定石墨物質之（〇 〇 2 )面的繞射波峰，由此 波峰位置算出 d ◦。2。算出方法係根據學振法（日本學術振 興會第 11 7委員會所定之方法），具體而言係根據記載於 12 312XP/發明說明書(補件)/93· 12/93129041 1258883 「碳纖維」（大谷杉郎著，第7 3 3〜7 4 2頁（1 9 8 6年），近代 編集社）等之方法所測定之值。 此外，本發明之複合粒子中，以該金屬之至少一部分接 觸於纖維狀石墨材料，且該等之至少外表面之一部分被碳 材料被覆者為佳。此處所謂之「被覆」，係指複合粒子之周 圍，亦即外表面之全部或一部分被碳材料包圍之構造。因 此，若滿足此種要件，碳材料之一部分可侵入於纖維狀石 墨所形成之立體内部，亦可接觸於該金屬。例如，亦包含 將金屬保持於互相穿插之纖維狀石墨中，再於其外表面之 一部分以碳材料被覆之構造等。此種複合粒子可確保吸收 膨脹之孔隙，同時維持導電性，於循環特性等方面優異， 因此特佳。又，此複合粒子進一步含有鱗片狀石墨者更佳。 其原因在於，鱗片狀石墨容易形成孔隙，且相較於纖維狀 石墨，其表面積較小，因此可提升循環特性與初期充放電 效率。此種鱗片狀石墨係以包圍保持金屬之纖維狀石墨之 狀態而捲入該複合粒子。 本發明之複合粒子之形狀係不特定，並無特別的限制。 複合粒子之平均粒徑以1 // m〜5 0 // m為佳。其原因在於， 於該範圍中，製作電極時複合粒子間存在充分的接點，得 以確保導電性，因此於循環特性方面特別優異。較佳為 3 // m〜3 0 // m。另夕卜，一般而言，使用於負極材料之一般用 途之較佳大小為3〜50//ηι左右。 複合粒子之比表面積以2 0 m2 / g以下為佳。其原因在於， 電解液與反應面積被限定，故初期充放電效率優異。以 13 312XP/發明說明書(補件)/93-12/93129041 1258883 0.5m2/g〜20m2/g為更佳。特佳為lm2/g〜10m2/g。比表面積 係以氮氣吸附BET法測定。 本發明之複合粒子之平均縱橫比（a s p e c t r a ΐ i 〇 )為 5 以下，又以3以下特佳。 (可與鋰合金化之金屬） 可與裡合金化之金屬可列舉如Al、Pb、Zn、Sn、Bi、In、 Mg、 Ga、 Cd、 Ag、 Si、 B、 Au、 Pt、 Pd、 Sb、 Ge、 Ni % o 又，亦可為此等金屬之2種以上之合金。合金中亦可進一 步含有上述以外之元素。又，金屬之一部分或全部亦可為 氧化物、氮化物、碳化物等化合物。較佳的該金屬有石夕 (S i )、錫（S η )，特佳者為矽。又，該金屬為結晶質或非結 晶質均可，但以非結晶質為佳。其原因在於，膨脹係等方 向地發生，因此對複合粒子之影響較小。 該金屬之形狀並無特別的限制，可為粒狀、球狀、板狀、 鱗片狀、針狀、線狀等任一者。亦可以膜狀存在於石墨材 料或碳材料之表面。其中較佳者為粒狀或球狀之粒子。 該金屬之平均粒徑以0 . 0 1 " m〜1 0 // m為佳。若為0. 01 // m 以上，該金屬之分散性變得充分。另一方面，若為 10//m 以下，容易吸收該金屬之膨脹。尤其以1 // m以下為佳。此 處，平均粒徑係指以雷射繞射式粒度計測定之累積度數為 5 0 %體積百分率之粒徑。 金屬以捲入於複合粒子之内部，而不存在於外表面為 佳。金屬存在於内部可較容易確保與石墨材料及/或碳材料 之接點，並提高導電性，可展現與金屬添加量相匹配的高 14 312XP/發明說明書(補件)/93-12/93129〇41 1258883 容量。 (碳材料） 碳材料具有導電性，作為黏合或被覆金屬與石墨材料者 係不可欠缺之成分，可經由將先質（p r e c u r s 〇 r )以最終未滿 1 5 Ο 0 °C之溫度熱處理而製造。本案中，碳材料亦有稱為碳 質材料之情況。碳材料只要實質上不含揮發份，並具有導 電性，且可吸留或脫離鋰離子者，可為任一種。碳材料之 先質之種類雖不限定，但於本發明中，以使用碳化後之碳 材料之殘碳率不同的2種以上為佳。此處，殘碳率係指以 J I S K 2 4 2 5之固定碳法為基準，加熱至8 0 0 °C使之實質上全 部被碳化時之殘餘部分，並以百分率表示之。殘碳率不同 係指多種的碳材料之間，殘碳率之相互差異在數％以上， 較佳為1 0 %以上。 碳材料之先質可列舉煤焦油、焦油輕油、焦油中油、焦 油重油、萘油、蒽油、煤焦遞青、遞青油、中間相（m e s 〇 p h a s e ) 遞青、氧交聯石油遞青、重油等石油系或煤碳系之焦油遞 青類；或具聚乙烯醇等熱可塑性樹脂類；酚樹脂、脲樹脂、 順丁烯二酸樹月旨、庫馬龍（c u m a r ο n e )樹月旨、二曱苯樹月旨、 σ夫喃樹脂等熱硬化性樹脂類。自同時抑制放電容量的降低 之觀點而言，特別以焦油瀝青類為佳。 殘碳率不同之2種以上之先質，例如可使用殘碳率1 0〜5 0 %之酚樹脂與殘碳率5 0〜9 0 %之煤焦油瀝青。 殘碳率相對較低之碳材料（碳材料 A )之先質，於加熱 後之碳材料中會產生較多的孔隙5因此可擔任主要形成金 15 312XP/發明說明書(補件)/93-12/93129041 1258883 屬周圍之孔隙的角色。另一方面，殘碳率相對較高之碳材 料（碳材料 B )之先質，於加熱後之碳材料中所產生的孔 隙較少，可形成緻密的碳材料，因此可擔任主要形成複合 粒子之最表層，且包圍複合粒子之角色。其結果為，使用 含有此之負極材料的鋰離子二次電池的不可逆容量得以減 低（初期充放電效率得以提升）。因此，於本發明之複合粒 子之製造過程中，首先將碳材料A之先質與金屬或石墨材 料混合而複合化後，再混合碳材料B之先質並複合化為佳。 (石墨材料） 石墨材料只要為可吸留及放出鋰離子者便可，並無特別 的限制。具體而言，有材料之一部分或全部為石墨質形成 者。例如有將焦油、瀝青類以最終1 5 0 0 °C以上之溫度熱處 理（石墨化）所得之人造石墨或天然石墨等。本案中，亦 有將石墨材料稱為石墨質材料之情況。更具體地說，可例 示將石油系或煤炭系之焦油瀝青類等具有易石墨化之性質 的碳材料，予以熱處理並聚縮合而成之中間相燒製體或中 間相小球體。亦可將焦炭類於 1 5 0 0 °C以上、較佳為 2 8 0 0〜3 3 0 0 °C下，石墨化處理而得。 石墨材料之形狀可為球狀、塊狀、板狀、鱗片狀、纖維 狀等任一者。尤其以鱗片狀或接近鱗片狀之形狀者、或纖 維狀者為佳。其理由係如上所述。又，亦可為上述各種之 混合物、造粒物、被覆物、層合物等。又，亦可為經於液 相、氣相、固相中施行各種化學處理、熱處理、氧化處理、 物理處理等者。 16 312XP/發明說明書(補件)/93-12/93129041 1258883 石墨材料之平均粒徑為1〜3 Ο // m、尤以 3〜1 5 // m為佳。 其原因在於，較容易製作具有上述之較佳平均粒徑之複合 粒子。 於本發明之複合粒子中使用鱗片狀石墨材料之情況，該 鱗片狀石墨材料以配置為無規狀（r a n d 〇 m )為佳。尤其是 配列為高麗菜狀、同心圓狀之狀態更佳。鱗片狀石墨之基 礎（basal)面（與邊緣面正交之面）向著複合粒子之外表 面側為佳，基礎面之一部分露出於複合粒子之外表面更佳。 於本發明之複合粒子中使用纖維狀石墨材料之情況，該 纖維狀石墨材料可為凝集狀態，亦可為解除凝集之分散狀 態，特別以將金屬粒子内包之凝集為綿狀之狀態為佳。由 於纖維狀石墨材料之比表面積大，因此，將具有流動性之 碳材料的先質與複合粒子混合時，該流動性先質會吸附於 構成複合粒子之該纖維狀碳材料之表面，不易滲透至複合 粒子内部，具有容易於被覆複合粒子内部確保孔隙之效果。 纖維狀石墨材料可藉由將先質於最終溫度 1 5 0 0〜3 3 0 0 °C 下熱處理而獲得。該先質只要為可得到纖維狀石墨材料 者，可為任一種，而尤其已可石墨化之纖維狀碳材料為佳。 例如可列舉碳奈米材料、碳奈米管或氣相成長碳纖維等。 該先質以短軸長（直徑）1〜5 Ο Ο n in為佳，又以1 0〜2 Ο Ο n m更 佳。又，該先質之縱橫比為5以上，尤以1 0〜3 0 0為佳。此 處，縱橫比係指纖維長/短轴長。 (複合粒子之製造） 以下，例示本發明之複合粒子之製造方法。於本發明之 17 312XP/發明說明書(補件)/93-12/93129041 1258883 方法中，至少使用可與鋰合金化之金屬、石墨材料、以及 殘碳率相對上不同的多種碳材料之先質作為原料。亦即， 例如可舉出將可與鋰合金化之金屬、石墨材料、以及殘碳 率相對較低的碳材料（碳材料A )之先質（先質A )混合， 再將所得之複合粒子與殘碳率相對較高之碳材料（碳材料 B )之先質（先質B )混合，再予以加熱之方法。於此製造 方法中，熱處理係以可使複合粒子之碳材料A及碳材料B 成為實質上不含有揮發物之狀態的溫度進行較佳。 此情況，若以質量百分率示出金屬、石墨材料及碳材料 之較佳組成’係金屬/石墨材料/碳材料二1〜50wt% / 3 0〜9 5 w t % / 4〜5 0 w t %之範圍。若該組成比為該範圍内，將 含有該複合粒子之負極材料使用於鋰離子二次電池時，該 電池之放電容量得以提升，且可得到該電池之循環特性的 改善效果。較佳係以成為 2〜3 0 w t % / 6 0〜9 3 w t % / 5〜3 0 w t % 之範圍的組成予以調配。具體而言，係為金屬/石墨材料/ 碳材料 A /碳材料 B二；1〜5 0 w t % / 3 5〜9 5 w t % / 2〜5 0 w t % /2〜40wt%之範圍，較佳為2〜30wt% / 60〜93wt% / 3〜30wt% / 2〜3 0 w t %之範圍。然而，於最終製品中，並無法區別來自 先質A、B之碳材料A、B。 藉由將該先質於6 0 0 °C以上、較佳為8 0 0 °C以上之溫度下 熱處理，使其被碳化，對碳材料賦予導電性。該熱處理可 階段性地分為數次進行，亦可於觸媒之存在下進行。又， 可於氧化性氣體、非氧化性氣體之任一環境中進行。 其中，於使用矽作為該金屬之情況，因於1 5 0 0 °C以上亦 18 312XP/發明說明書(補件)/93-12/93129041 1258883 有碳與；s夕發生反應而生成S i C之可能，故加熱 1 5 0 0 °C為佳。通常，以 1 0 0 0〜1 2 0 0 °C為佳。又 地使用分散媒予以混合。分散媒於先質A或先j 不分解之溫度以下去除為佳。 又，於熱處理之前後的任一階段中，最好適 碎、篩分、分級，進行除去微粉末等之粒度調 在以較低溫度熱處理，且上述複合體具有柔 下，可增加使複合體轉動之操作或賦予高剪切 如此一來，複合體會成為接近球狀之形狀，特 片狀石墨做為石墨材料之一的情況，該鱗片狀 置為同心圓狀，為較佳情況。可進行此種操作 使用GRANUREX (富羅因產業（股）製）、NEW-(清新企業（股）製）、AGROMASTER (細川米克 等之造粒機；輥磨、Η Y B R I D I Z A T I 0 N S Y S T E Μ ( 作所（股）製）、MECHANO MICORSYSTEM (奈良 (股）製）、MECHANOFUSION SYSTEM (細川米克 等之壓縮剪切式加工裝置等。 此外，亦可於進行最終熱處理之前，將同種 材料之先質多層被覆於該複合體之外表面。 做為其他的製造方法，可例示預先將碳材料 於石墨材料上，與該金屬混合後再熱處理之方 可採用將該金屬埋設或被覆於石墨材料後，與 質混合再熱處理之方法等。此時，作為以氣相 該金屬之有機化合物附著於石墨材料之方法， 312XP/發明說明書(補件)/93-12/93129041 溫度以未滿 ，最好適當 賢B不軟化、 當地經由粉 整。另夕卜， 軟性之狀態 力之操作。 別於使用鱗 石墨容易配 之裝置，可 GRA MACHINE 龍（股）製） 奈良機械製 機械製作所 龍（股）製） 或異種之碳 的先質附著 法。或者， 碳材料之先 將該金屬或 可列舉真空 19 1258883 沈積法、滅鑛法、離子鑛法（i ο η p 1 a t i n g )、分子射線磊 晶法等之 PVD( Physical Vapor Deposition)法，或常壓 CVD ( Chemical Vapor Deposition)法、減壓 CVD法、電 漿 CVD 法、MO ( Magneto-optic) CVD 法、光 CVD 等之 CVD 法。 又，於使用鱗片狀石墨之情況，可採用預先將該鱗片狀 石墨予以球狀化後，於孔隙中注入、含浸碳材料之先質與 金屬之液狀混合物，將碳材料之先質予以混合並熱處理之 方法等。 又，於使用纖維狀石墨之情況，可採用將該金屬與該纖 維狀石墨預先一體化後，混合碳材料之先質並熱處理之方 法等。於該金屬與該纖維狀石墨之一體化、或其後之熱處 理之階段等中，亦可共存有鱗片狀石墨。作為將該金屬與 該纖維狀石墨一體化之方法，可採用賦予例如壓縮、剪切、 衝撞、摩擦等之機械性能量的機械化學 (mechano - chemical)處理，或將該金屬粒子投入分散有 纖維狀石墨質材料之有機溶劑中後，再去除有機溶劑之方 法等。 使用本發明之複合粒子製作負極材料•負極時，亦可於 負極材料之製作中共存有通常使用之導電材、改質材、添 加劑等。例如，可添加天然石墨、人造石墨、中間相燒製 體石墨化合物、中間相纖維體石墨化合物等之各種石墨材 料，以及非晶質硬碳（h a r d c a r b ο η )等碳材料、碳黑或氣 相成長碳纖維等導電助材、酚樹脂等之有機物、矽等金屬、 氧化錫等金屬化合物。該等之添加量通常係相對於複合粒 20 312ΧΡ/發明說明書(補件)/93-12/93129041 1258883 子以Ο . 1〜5 0質量％之總量。 本發明係含有上述複合粒子之鋰離子二次電池用負極材 料，以及使用該負極材料之鋰離子二次電池。 (負極） 本發明之鋰離子二次電池用之負極，係以通常之負極成 形方法為基準而製作，但只要為可得到化學性、電化學性 安定的負極之方法，並無任何限制。於負極之製作時，最 好於本發明之複合粒子中加入結合劑，使用預先調製之負 極混合劑。結合劑以對於電解質顯現化學及電化學安定性 者為佳。例如使用聚四氟乙烯、聚偏二氟乙烯等之氟系樹 脂粉末；聚乙烯、聚乙烯醇等之樹脂粉末；羧曱基纖維素 等。亦可併用該等。結合劑通常係以負極混合劑之總量中 的1〜2 0 w t %左右之比例使用。 更具體地例示，首先，將本發明之複合粒子以分級等調 整為所需之粒度，將與結合劑混合所得之混合物分散於溶 劑中，製成糊狀（p a s t e )而調製負極混合劑。亦即，將本 發明之複合粒子和結合劑與水、異丙醇、N -曱基吡咯酮、 二曱基曱酿胺等溶劑混合所得之糊漿（s 1 u r r y )，利用公知 的授拌機、混合機、混練機、捏和機等予以攪：拌混合，調 製糊狀物。將該糊狀物塗佈於集電材之單面或雙面並將之 乾燥，即可得到負極混合劑層均勻且強力黏著之負極。負 極混合劑層之膜厚為1 0〜2 0 0 // m，較佳為2 0〜1 0 0 " m。 又，本發明之負極亦可將本發明之複合粒子與聚乙烯、 聚乙烯醇等樹脂粉末乾式混合，於模具内熱壓成型而製作。 21 312XP/發明說明書(補件)/93-12/93129041 1258883 於形成負極混合劑層後進行壓合等之壓著，則可更提高 負極混合劑層與集電體之黏著強度。 使用於負極之製作的集電體之形狀，並無特別的限制。 較佳者有箔狀、網目狀等。網目狀者可列舉展成金屬 (expanded metal )等。集電體之材質以銅、不錄鋼、錄 等為佳。集電體之厚度，在箔狀之情況以5〜2 0 // m左右為 佳。 另外，本發明之負極亦可於含有可與鋰合金化之金屬、 石墨材料與碳材料之複合粒子中，進一步調配天然石墨等 石墨材料，乃至非晶質硬碳等之碳材料、酚樹脂等之有機 物、矽等之金屬、氧化錫等之金屬化合物等。 (裡離子二次電池） 鋰離子二次電池通常以負極、正極以及非水電解質做為 主要電池構成要素。由於正極與負極分別成為鋰離子之載 持體，故成為充電時鋰離子吸留於負極中、放電時自負極 脫離之電池機構。 本發明之鋰離子二次電池，除了使用本發明之負極材料 作為負極材料之外，並無特別的限制，正極、電解質、分 隔片等其他電池構成要素，係以一般鋰離子二次電池之要 素為準。 (正極） 正極係經由將例如由正極材料與結合劑及導電劑所構成 之正極混合劑塗佈於集電體之表面而形成。正極之材料（正 極活性物質）以選擇可吸留/脫離充足量的鋰者為佳，有： 22 312XP/發明說明書(補件)/93-12/93129041 1258883 含有經之過渡金屬氧化物、過渡金屬硫族（c h a 1 c 〇 g e η )化 物、鈒氧化物及其經化合物等之含有裡之化合物、一般式 MxM〇6S8-Y(式中，Μ為至少一種之過渡金屬元素，X為0SX S4，Y為0SYS1之範圍之數值）所示之歇布雷爾相化合 物、活性碳、活性碳纖維等。ί凡氧化物有以 V 2 0 5、V 6 0 1 3、 V2〇4、V3〇8 所示者。 含有鋰之過渡金屬氧化物為鋰與過渡金屬之複合氧化 物，亦可為將鋰與2種類以上之過渡金屬固溶而成者。複 合氧化物可單獨使用，亦可組合2種類以上使用。含有鋰 之過渡金屬氧化物’具體而言係以L i Μ 1 1 - X Μ 2 X 0 2 (式中Μ 1、 Μ2係至少一種之過渡金屬元素，X為0 S X S 1之範圍之數 值）或L i Μ 12 - γ Μ 2 γ 0 4 (式中Μ 1、Μ2係至少一種之過渡金屬元 素，Υ為0$Υ$2之範圍之數值）所示者。 Μ1、Μ2所示之過渡金屬元素，有Co、Ni、Mn、Cr、Ti、 V、 Fe、 Zn、 Al、 In、 Sn 等，較佳者為 Co、 Fe、 Μη、 Ti、 Cr、V、A 1 等。較佳之具體例為 LiCo〇2、LiNi〇2、LiMn〇2、 LiNio.9Coo.1O2、LiNio.5Mno.5O2 等。 含有鋰之過渡金屬氧化物可例如以鋰、過渡金屬之氧化 物、氫氧化物、鹽類等作為起始原料，將此等起始原料根 據所需之金屬氧化物之組成予以混合，於氧環境下以 6 0 0〜1 0 0 0 °C之溫度燒製而得。 正極活性物質可單獨使用上述化合物，亦可併用2種類 以上。例如，可於正極中添加碳酸鋰等之碳酸鹽。又，於 形成正極時，亦可適當使用向來周知之導電劑或結合劑等 23 312XP/發明說明書(補件)/93-12/93129041 1258883 各種添加劑。 正極之製作係將由上述正極材料、結合劑、以及用以對 正極賦予導電性之導電劑所構成之正極混合劑，塗佈於集 電體之兩面而形成正極混合劑層。結合劑可使用與製作負 極時所用之相同者。導電劑可使用石墨化物、碳黑等周知 者。 集電體之形狀並未特別限定，可使用箔狀或網目、展成 金屬等網狀者。集電體之材質有鋁、不銹鋼、鎳等。以厚 度為10〜40// m者為佳。 正極係與負極相同，可將正極混合劑分散於溶劑中成為 糊狀，再將此糊狀之正極混合劑塗佈於集電體並乾燥，以 形成正極混合劑層，亦可於形成正極混合劑層後，再進行 壓合加壓等壓黏。藉此，正極混合劑層可均勻化並強力地 接黏於集電材。 (非水電解質） 使用於本發明之鋰離子二次電池之非水電解質為通常使 用於非水電解液之電解質鹽，可使用例如 L i P F 6、L i B F 4、 L1AsF6 、 LiClO. 、 LiBCCeHs) 、 LiCl 、 LiBr 、 LiCFaSOa 、 LiCHsSCh、LiN(CF3S〇2)2、LiC(CF3S〇2)” LiN(CF3CH2〇S〇2)2、 LiN(CFsCF2〇S〇2)2 、 L i N ( H C F 2 C F 2 C H 2 0 S 0 2) 2 、1258883 IX. Description of the Invention: [Technical Field] The present invention relates to a composite particle which combines a metal which can be alloyed with lithium with a graphite material and a carbon material, and a negative electrode material of a lithium ion secondary used therewith. , negative electrode and lithium ion secondary battery. [Prior Art] A lithium ion secondary battery has a high voltage energy density compared to other secondary batteries, and thus is widely used as a power source for electronic equipment. In recent years, miniaturization and high performance of sub-machines have progressed rapidly, and the expectation of further increasing the energy density of lithium secondary batteries has been increasing. At present, the ionic secondary battery is generally used in the positive electrode using L i C 〇 0 2 , and the electrode is used in the pole. However, the graphite negative electrode is excellent in reversibility of charge and discharge. The discharge capacity has reached a value close to that of the interlayer compound (L i C 6 ) (37 2 mAh/g). Therefore, in order to further increase the density of the battery, it is necessary to develop a negative electrode material having a larger discharge capacity than graphite. Metallic lithium has the largest discharge capacity as a negative electrode material. However, in the case of electricity, lithium precipitates in a dendritic state and deteriorates the negative electrode, so that the electric charge and discharge cycle becomes short. Further, there is also a lithium-separated sheet which is precipitated in a dendritic shape and reaches the positive electrode, which may cause a short circuit of the battery. Therefore, alloys or metal compounds which are formed with lithium as a negative electrode material for lithium metal have been reviewed. The discharge capacity of these alloy negative electrodes is small in lithium, but far exceeds graphite. However, the pulverization of the active material with the expansion of the alloy is accompanied by the cycle characteristics of the lithium ion secondary. 312XP / invention manual (supplement) /93-12/93129041 / or battery, south, electric ion in negative, its value energy in the filling pool of gold than the gold body battery 1258883 to solve the alloy as described above The shortcomings of the negative electrode, the development of a negative electrode made of a composite of a metal or a metal compound and a graphite material and/or a carbon material are being reviewed. In order to absorb the expansion accompanying the alloying, there is a method in which the pore system is effective in the composite. However, if the pores are too much, the strength or conductivity of the composite material may be lowered. That is, the relationship between the amount of voids of the composite material and the resistance of the material itself is related to the conductivity (a n t i η 〇 m y ), and it is extremely difficult to balance the two and perfectly meet the requirements. For example, Japanese Laid-Open Patent Publication No. 3 369 594 discloses a composite material comprising a metal material which can be alloyed with an alkali metal such as lithium, a graphite material and a carbon material. In this composite material, the carbon material acts as a bonding or coating metal material and graphite material. The D band of the surface of the carbon material measured by the Raman ray spectrophotometry using argon laser 1 3 6 0 c η Τ 1 peak intensity ID and G band 1 5 8 0 c π Γ 1 peak intensity IG The ratio ID / IG (R value) is displayed as 0 · 4 or more. It shows that the carbon material is not graphitized. However, in the case of the composite material, the carbon material also penetrates into the interior of the composite material, so that the volume expansion of the metal material and lithium alloying cannot be prevented from damaging the composite material, and the cycle characteristics are still lowered. On the other hand, a negative electrode material in which a part of the surface of the ruthenium-containing particle or the entire surface of the fiber-like carbon is fixed is disclosed in Japanese Laid-Open Patent Publication No. 2000-167. The purpose of this technique is to ensure the conductivity between the ruthenium particles by the fibrous carbon even if the ruthenium particles shrink during discharge. However, in this configuration, although the conductivity 5 is maintained, the metal expansion which occurs during charging cannot be absorbed, resulting in a decrease in cycle characteristics. 6 312 ΧΡ / invention manual (supplement) / 93-12/93129041 1258883 Japanese Patent No. 3 4 6 6 5 7 6 discloses a negative electrode comprising carbon-coated porous particles composed of carbon-containing particles, The carbonaceous particles correspond to a graphite material. Although the negative electrode material is actively made porous, the structure of the negative electrode material is broken due to volume expansion of ruthenium and lithium, and the cycle characteristics are still unsatisfactory. Further, since the carbonaceous particles (the stone is as small as 1 // m or less, the decomposition reaction of the electrolytic solution is likely to occur, and the electrical efficiency is also lowered. As described above, in the prior art, it is difficult to maintain the maintenance of the expansion property. The present invention provides a lithium pool which can achieve a large discharge capacity and excellent cycle characteristics when a composite particle containing three components such as a metal which can be alloyed with lithium and a graphite material is used for a lithium ion secondary battery. And the charge and discharge efficiency. In other words, the present invention aims to provide the novel composite particles of the three properties of the sub-secondary battery, and the negative electrode material of the ion secondary battery, the negative electrode and the ion secondary. [Invention] The present invention relates to a a composite particle which is capable of contacting at least a portion of the genus Lithium with a material selected from the group consisting of graphite and a carbon material, and the pores surrounding the metal contain the metal, the graphite material, and the carbon material above the total pores In addition, it is preferable that the composite material is at least one material of a group consisting of graphite and fibrous graphite. The specification (supplement)/93-12/93129041 contains hair particles and materials. In another example, the method of alloying obtains the ink material, so the initial absorption and the conductive ion secondary material and the carbon material The anode material is excellent in the initial stage to satisfy the lithium battery. At least 1 of the alloyed gold group is 2 0 v ο 1 % composite particles. From the scaly shape 7 1258883 In addition, in the composite particles, when the graphite material is scaly, the ratio of the peak intensity of the D-band of the Raman spectrum to the peak intensity of the G-band is less than zero.  4 is better. Further, in the composite particles, the graphite material has an average lattice plane spacing d 〇 〇 2 obtained by X-ray diffraction at 0.  Fibrous graphite of 3 4 n m or less is preferred. Further, in any of the above composite particles, at least a part of the metal is in contact with the fibrous graphite, and at least one of the outer surfaces is preferably coated with a carbon material. Further, the composite particles further preferably contain flaky graphite. Further, in any of the above composite particles, the metal is preferably Shi Xi. Further, in any of the above composite particles, the average particle diameter of the metal is 0. 01 ~ 10 / / m is better. Further, in any of the above composite particles, the metal is preferably amorphous. Further, in any of the above composite particles, the specific surface area of the composite particles is preferably 20 m 2 /g or less. Further, in any of the above composite particles, the average particle diameter of the composite particles is preferably from 1 to 50 // m. Further, in the present invention, a negative electrode material for a lithium ion secondary battery containing any of the above composite particles is provided. Further, a negative electrode for a lithium ion secondary battery using the negative electrode material for a lithium ion secondary battery is also provided. Further, a lithium ion secondary battery using the negative electrode for a lithium ion secondary battery is also provided. Moreover, in the present invention, an invention of a composite particle is provided in a composite particle in which a graphite material is integrated with a metal which can be alloyed with lithium by a carbon material, characterized in that the composite particle has pores, and Metal 8 3 12XP/Invention Manual (Supplement)/93-] 2/93129041 1258883 The ratio of the pores in the periphery to the total pores of the composite particles is 2% or more. [Embodiment] Hereinafter, the present invention will be more specifically described. As described above, in the conventional metal-graphite (carbon) type composite material, the decrease in cycle characteristics caused by the expansion of the metal in the negative electrode when forming an alloy with lithium cannot be avoided. Therefore, the inventors of the present invention have lifted off the conductivity of the negative electrode while studying the negative electrode which can absorb the expanded structure. As a result, it has been found that merely increasing the total pores of the composite particles cannot maintain the conductivity of the negative electrode. However, if pores absorbing the expansion are formed around the constituent metal, the powder of the negative electrode can be prevented from being pulverized or peeled off while maintaining the conductivity of the negative electrode. Thus the present invention has been completed. (Composite Particles) The composite particles of the present invention are in contact with at least a portion of a metal alloyable with lithium and at least one material selected from the group consisting of graphite materials and carbon materials, and the pores around the metal are relative to the total pores. 2 Ο ν ο 1 % or more of composite particles containing the metal, the graphite material, and the carbon material. In the composite particles, at least a portion of the metal is in contact with both the graphite material or the carbon material or the graphite material and the carbon material, and the pores around the metal are also in contact with at least a portion of the metal surface. Usually, the composite particles are dispersed and coated with a plurality of the metal particles, and are dispersed to contain a plurality of pores of a specific size. In the present invention, the ratio of the pores around the metal (hereinafter also referred to as the peripheral pores) to the total pores of the composite particles must be 2 Ο ν ο 1 % or more. If 9 312 ΧΡ / invention specification (supplement) / 93-12/93129 〇 41 1258883 full 2 Ο ν ο 1 %, the expansion of the metal when forming an alloy with lithium cannot be absorbed. The preferred peripheral porosity is 4 Ο ν ο 1 % or more, and the preferred peripheral porosity is 5 Ο ν ο 1 % or more. In addition, theoretically, the upper limit of the surrounding porosity of the metal may be 100%. At this time, the state in which the pores in the composite particles are all in contact with the metal portion is exhibited. This case does not exclude this situation. However, in general, in the composite particles of the present invention, the upper limit of the peripheral porosity is preferably 80 to 90 vol%. Further, in the composite particles of the present invention, the ratio of the total pores to the total volume is preferably 3 to 50 vol%. The reason for this is that, in general, when it is 3 vol% or more, the volume expansion due to alloying can be sufficiently absorbed, and if it is 5 0 ν ο 1 % or less, the strength of the composite particles can be sufficiently maintained. It is especially good at 3 0~5 0 ν ο 1 %. The volume (c a p a c i t y ) of the total pores of the composite particles of the present invention can be obtained, for example, by measuring the composite particles pulverized and exposing the cross section by a mercury porosimeter. Further, the porosity (volume ratio) of the entire composite particles can be calculated therefrom. In the present invention, the ratio of the pores around the metal to the total pores of the composite particles as a whole can be obtained by the following method. Using a scanning electron microscope, 50 composite particles were arbitrarily selected, and a cross-sectional photograph was taken at a magnification of 400 times. From this cross-sectional photograph, the total value of the total pore area of each composite particle and the total value of the surrounding pores of each metal were obtained. Using the 50 values of these composite particles, the ratio of the area of the pores around the metal to the total pore area (area ratio) was determined, and the arithmetic mean was each composite particle, and this value was taken as the surrounding porosity of the metal of the present invention. From the cross-sectional photograph, it can be judged whether at least a part of the metal is in contact with the graphite material and/or the carbon material. In addition, the mass composition of the composite particles is based on the metal, and after the composite particle ash 10 312XP/invention specification (supplement)/93-12/93129041 1258883, elemental analysis is performed by luminescence spectroscopy, and the value converted to the concentration of the metal is taken. . The graphite material and the carbon material were magnified by a polarizing microscope, and the cross section of the composite particles was magnified to 100 times and photographed, and the appearance of any 10 composite particles was observed, and the difference in appearance due to the high crystallinity was judged. Further, the ratio between the two is an average value of the ratio of the area of the graphite material to the area of the carbon material inside the particle. Further, the ratio of the area occupied by the graphite material to the carbon material can be obtained by observing a thin section of the composite particle and observing it using a transmission electron microscope. Here, although the ratio of the area of the graphite material to the carbon material is obtained, since the density of the graphite material and the carbon material are not greatly different, in the present invention, the area ratio and the mass ratio obtained in the above manner are almost the same. . Since the above-mentioned pores are present around the above-mentioned metal in the composite particles of the present invention, the cycle characteristics of the lithium ion secondary battery can be improved. This is because the expansion of the metal is absorbed by the pores during charging, and the structural damage of the negative electrode material containing the composite particles can be suppressed. That is, even when the metal itself is powdered, the form of the composite particles of the entire negative electrode material is maintained, so that the contact between the composite particles is maintained without impairing the current collecting property. Therefore, it is presumed that it can suppress the decrease in cycle characteristics. In the composite particles of the present invention, the graphite material constituting the composite particles is preferably scaly or fibrous. If the graphite material is in the form of scales, it is easy to form pores in the composite particles, and in particular, it is possible to improve cycle characteristics and the like. Further, in the composite particle of the present invention, when the graphite material is scaly, the composite particle is in the Raman spectrum D band 11 312XP / invention specification (supplement) / 93-12/93129041 1258883 domain peak intensity (ID) The ratio of the peak intensity (IG) relative to the G band (ID/IG) is less than 0. 4 is better. If using wavelength 514. The 5 nm argon laser is used to determine the Raman spectrum of the composite particles. The ratio of the peak intensity (ID) of the D-band to the peak intensity (IG) of the G-band (ID / IG ) can be used to determine the outer surface of the composite particle. Crystallinity. The I D / I G ratio is generally referred to as "R value", and the composite particle of the present invention has an R value of less than 0.  4 is better. In addition, the G band is usually observed at 1 5 80 c ηΤ 1 and the D band is observed at 1 3 6 0 π Γ 1 , and can be observed in the region of ± 2 0 c π Γ 1 according to the measurement error. By satisfying the structure of the above composite particles, it is possible to obtain an R value of less than 0.  4 composite particles. Such composite particles are particularly excellent in surface crystallinity, excellent in cycle characteristics and initial charge and discharge efficiency, and the like. In addition, the preferred range of R values is 0.  1 5~0.  3 8, better range is 0· 2 ~ 0.  3. In addition, the R value shows 0.  In the case of 4 or more, for example, a graphite material other than scaly graphite is used for the graphite material, and the edge surface of the graphite is exposed to the outer surface. On the other hand, if the graphite material is fibrous, the conductivity in the composite particles can be improved, and in particular, the cycle characteristics can be improved. Further, in the composite particles of the present invention, when the graphite material is fibrous, the average lattice spacing d of the X-rays of the fibrous graphite is refracted. ϋ 2 at 0.  3 4 n m or less is preferred. Such fibrous graphite is particularly excellent in crystallinity and large in discharge capacity. Further, the measurement of the lattice spacing was performed by using C u Κ α ray as an X-ray source and high-purity 矽 as a standard substance, and measuring a diffraction peak of the (〇 〇 2 ) plane of the graphite substance, thereby calculating d ◦ at the peak position. 2. The calculation method is based on the Xue Zhen method (the method set by the 11th Committee of the Japan Society for the Promotion of Science), specifically, according to the description in 12 312XP / Invention Manual (supplement) / 93· 12/93129041 1258883 "Carbon Fiber" (Great Sequoia) Lang, the value measured by the method of 7 3 3~7 4 2 (1 1986), Modern Co., Ltd.). Further, in the composite particles of the present invention, at least a part of the metal is in contact with the fibrous graphite material, and at least one of the outer surfaces is preferably covered with a carbon material. The term "coating" as used herein refers to a structure in which the composite particles are surrounded, that is, a structure in which all or a part of the outer surface is surrounded by a carbon material. Therefore, if such a requirement is satisfied, a part of the carbon material may intrude into the three-dimensional interior formed by the fibrous graphite or may be in contact with the metal. For example, it also includes a structure in which a metal is held in fibrous graphite interpenetrated with each other, and a part of the outer surface thereof is covered with a carbon material. Such a composite particle is excellent in that it absorbs the expanded pores while maintaining conductivity and is excellent in cycle characteristics and the like. Further, it is more preferable that the composite particles further contain flaky graphite. The reason for this is that flaky graphite is easy to form pores, and its surface area is smaller than that of fibrous graphite, so that cycle characteristics and initial charge and discharge efficiency can be improved. Such scaly graphite is wound into the composite particles in a state of surrounding the fibrous graphite of the metal. The shape of the composite particles of the present invention is not particularly limited and is not particularly limited. The average particle size of the composite particles is preferably from 1 // m to 5 0 // m. This is because, in this range, when the electrode is formed, a sufficient contact exists between the composite particles, and conductivity is ensured, which is particularly excellent in cycle characteristics. Preferably, it is 3 // m~3 0 // m. Further, in general, a preferred size for the general use of the negative electrode material is about 3 to 50 / / ηι. The specific surface area of the composite particles is preferably 20 m 2 /g or less. This is because the electrolyte solution and the reaction area are limited, so that the initial charge and discharge efficiency is excellent. To 13 312XP / invention manual (supplement) / 93-12/93129041 1258883 0. 5m2/g~20m2/g is more preferable. Particularly preferred is lm2/g to 10 m2/g. The specific surface area was measured by a nitrogen adsorption BET method. The composite particles of the present invention have an average aspect ratio (a s p e c t r a ΐ i 〇 ) of 5 or less, and particularly preferably 3 or less. (Metals which can be alloyed with lithium) Metals which can be alloyed with, for example, Al, Pb, Zn, Sn, Bi, In, Mg, Ga, Cd, Ag, Si, B, Au, Pt, Pd, Sb , Ge, Ni % o In addition, it is also possible to use two or more alloys of such metals. The alloy may further contain elements other than the above. Further, part or all of the metal may be a compound such as an oxide, a nitride or a carbide. Preferably, the metal has Si Xi (S i ), tin (S η ), and particularly preferred. Further, the metal may be crystalline or non-crystalline, but is preferably amorphous. The reason for this is that the expansion system or the like occurs in a direction, and thus the influence on the composite particles is small. The shape of the metal is not particularly limited, and may be any of a granular shape, a spherical shape, a plate shape, a scale shape, a needle shape, and a linear shape. It may also be present in the form of a film on the surface of a graphite material or a carbon material. Preferred among these are granular or spherical particles. The average particle size of the metal is 0.  0 1 " m~1 0 // m is better. If it is 0.  01 / m or more, the dispersibility of the metal becomes sufficient. On the other hand, if it is 10 / / m or less, it is easy to absorb the expansion of the metal. Especially below 1 // m is preferred. Here, the average particle diameter means a particle diameter which is measured by a laser diffraction type particle size meter and has a cumulative degree of 50% by volume. It is preferable that the metal is entangled inside the composite particles without being present on the outer surface. The presence of metal in the interior makes it easier to ensure contact with the graphite material and/or the carbon material, and to improve the conductivity, which can be displayed in accordance with the amount of metal added. 14 312XP / invention manual (supplement) / 93-12/93129 〇41 1258883 Capacity. (Carbon material) Carbon material is electrically conductive and can be used as a component that is indispensable for bonding or coating metal and graphite materials. It can be produced by heat-treating a precursor (precurs 〇r ) at a temperature of less than 15 Ο 0 °C. . In this case, carbon materials are also known as carbonaceous materials. The carbon material may be any one which is substantially free of volatile matter and has electrical conductivity and can be occluded or desorbed from lithium ions. The type of the carbon material is not limited, but in the present invention, it is preferred to use two or more types of carbon materials having a carbon residue after carbonization. Here, the residual carbon ratio means a residual portion which is heated to 80 ° C and is substantially completely carbonized based on the fixed carbon method of J I S K 2 4 2 5 and expressed as a percentage. The residual carbon ratio is different between the plurality of carbon materials, and the residual carbon ratio differs by several % or more, preferably by more than 10%. The precursors of carbon materials include coal tar, tar light oil, tar medium oil, tar heavy oil, naphthalene oil, eucalyptus oil, coal coke bluing, distilling oil, mesophase (mes 〇phase) advancing, oxygen cross-linking oil delivery Petroleum or carbon-based tar, such as green and heavy oil; or thermoplastic resin such as polyvinyl alcohol; phenol resin, urea resin, maleic acid tree, cumar ο ne tree Thermosetting resins such as korea, bismuth benzene, and sigma resin. From the viewpoint of suppressing the decrease in discharge capacity at the same time, tar pitch is particularly preferred. For the precursor having two or more kinds of residual carbon ratios, for example, a phenol resin having a residual carbon ratio of 10 to 50% and a coal tar pitch having a residual carbon ratio of 50 to 90% can be used. The carbon material (carbon material A) with a relatively low residual carbon ratio is the precursor of the carbon material in the heated carbon material. Therefore, it can be used as the main gold 15 312XP/invention specification (supplement)/93- 12/93129041 1258883 is the role of the surrounding pores. On the other hand, the carbon material (carbon material B) with a relatively high residual carbon ratio has a small amount of pores in the heated carbon material, and can form a dense carbon material, so that it can serve as a main composite particle. The outermost layer and the role of the composite particle. As a result, the irreversible capacity of the lithium ion secondary battery using the negative electrode material containing this is reduced (the initial charge and discharge efficiency is improved). Therefore, in the production process of the composite particles of the present invention, first, the precursor of the carbon material A is mixed with a metal or a graphite material to be composited, and then the precursor of the carbon material B is mixed and preferably combined. (Graphite material) The graphite material is not particularly limited as long as it can absorb and release lithium ions. Specifically, some or all of the materials are graphite formers. For example, there are artificial graphite or natural graphite obtained by heat-treating (graphitizing) tar and pitch at a temperature of at least 150,000 °C. In this case, the graphite material is also referred to as a graphite material. More specifically, a mesophase fired body or an intermediate phase small sphere obtained by heat-treating and condensing a carbon material having a property of being easily graphitized, such as petroleum-based or coal-based tar pitch, can be exemplified. The coke may be obtained by graphitization at a temperature of 150 ° C or higher, preferably 2 800 ° to 300 ° C. The shape of the graphite material may be any of a spherical shape, a block shape, a plate shape, a scale shape, and a fiber shape. In particular, those having a scaly shape or a shape close to a scaly shape or a fiber shape are preferred. The reason is as described above. Further, it may be a mixture, a granule, a coating, a laminate or the like of the above various kinds. Further, various chemical treatments, heat treatments, oxidation treatments, physical treatments, and the like may be carried out in the liquid phase, the gas phase, and the solid phase. 16 312XP/Invention Manual (Repair)/93-12/93129041 1258883 The average particle size of the graphite material is 1~3 Ο // m, especially 3~1 5 // m. The reason for this is that it is easier to produce composite particles having the above preferred average particle diameter. In the case where a flaky graphite material is used in the composite particles of the present invention, the flaky graphite material is preferably arranged in a random shape (r a n d 〇 m ). In particular, it is better to be in a state of Korean cuisine and concentric. The basal surface of the scaly graphite (the surface orthogonal to the edge surface) is preferably toward the outer surface of the composite particle, and one of the base surface is exposed to the outer surface of the composite particle. In the case where a fibrous graphite material is used in the composite particles of the present invention, the fibrous graphite material may be in agglomerated state or in a dispersed state in which agglomeration is released, and in particular, a state in which the metal particles are encapsulated into a cotton form is preferable. Since the fibrous graphite material has a large specific surface area, when the precursor of the fluid carbon material is mixed with the composite particles, the fluid precursor is adsorbed on the surface of the fibrous carbon material constituting the composite particles, and is not easily penetrated. Inside the composite particles, it is easy to ensure the pores inside the coated composite particles. The fibrous graphite material can be obtained by heat treatment at a final temperature of 1 500 to 3300 °C. The precursor may be any one as long as it can obtain a fibrous graphite material, and particularly a fibrous carbon material which can be graphitized. For example, a carbon nanomaterial, a carbon nanotube, or a vapor-grown carbon fiber can be mentioned. The precursor is preferably 1 to 5 Ο in n in short axis length (diameter), and more preferably 1 0 to 2 Ο Ο n m. Further, the aspect ratio of the precursor is 5 or more, and particularly preferably 10 to 300. Here, the aspect ratio refers to the fiber length/short axis length. (Manufacturing of Composite Particles) Hereinafter, a method for producing the composite particles of the present invention will be exemplified. In the method of the invention, the 312XP/invention specification (supplement)/93-12/93129041 1258883 method uses at least a precursor of a plurality of carbon materials which are alloyed with lithium, a graphite material, and a carbon residue having a relatively different residual carbon ratio. As a raw material. That is, for example, a metal which can be alloyed with lithium, a graphite material, and a precursor (precursor A) of a carbon material (carbon material A) having a relatively low residual carbon ratio are mixed, and the obtained composite particles are further obtained. It is mixed with the precursor (precursor B) of the carbon material (carbon material B) having a relatively high residual carbon ratio, and then heated. In this production method, the heat treatment is preferably carried out at a temperature at which the carbon material A and the carbon material B of the composite particles are substantially free of volatiles. In this case, if the mass, the preferred composition of the metal, the graphite material, and the carbon material is shown as 'metal/graphite material/carbon material 2 1 to 50 wt% / 3 0 to 9 5 wt % / 4 to 5 0 wt % range. When the composition ratio is within this range, when the negative electrode material containing the composite particles is used in a lithium ion secondary battery, the discharge capacity of the battery is improved, and the cycle characteristics of the battery can be improved. Preferably, the composition is made up to a range of 2 to 3 0 w t % / 6 0 to 9 3 w t % / 5 to 3 0 w t %. Specifically, it is a metal/graphite material/carbon material A/carbon material B2; 1~5 0 wt% / 3 5~9 5 wt% / 2~5 0 wt % /2~40 wt% range, Preferably, it is in the range of 2 to 30 wt% / 60 to 93 wt% / 3 to 30 wt% / 2 to 3 0 wt%. However, in the final product, it is impossible to distinguish the carbon materials A and B from the precursors A and B. The carbonaceous material is carbonized by heat treatment at a temperature of 60 ° C or higher, preferably at 80 ° C or higher, to impart conductivity to the carbon material. The heat treatment can be carried out in stages, in the presence of a catalyst. Further, it can be carried out in any of an oxidizing gas or a non-oxidizing gas. Wherein, in the case of using ruthenium as the metal, since 1500 °C or above is also 18 312XP / invention specification (supplement) / 93-12 / 93129941 1258883 carbon has a reaction with S s to generate S i C It is possible, so heating at 1 500 °C is preferred. Usually, it is preferably 1 0 0 0~1 2 0 0 °C. Further, the dispersion medium is used for mixing. It is preferred that the dispersing medium is removed below the temperature at which the precursor A or the first j is not decomposed. Further, in any stage after the heat treatment, it is preferable to suitably crush, sieving, classify, remove the fine powder, and the like, and adjust the particle size to heat treatment at a lower temperature, and the above composite has a softening, which can increase the composite. In the case of the operation of turning or imparting high shear, the composite body becomes a nearly spherical shape, and the tabular graphite is used as one of the graphite materials, and the scale is set to be concentric, which is preferable. This operation can be carried out using GRANUREX (Froin Industries Co., Ltd.), NEW- (fresh company (share) system), AGROMASTER (Hosokawa Mickey, etc. granulator; roll mill, Η YBRIDIZATI 0 NSYSTE Μ (manufactured by the company), MECHANO MICORSYSTEM (manufactured by Nara Corporation), MECHANOFUSION SYSTEM (compressed shear processing equipment such as Hosokawa Mickey, etc. In addition, the precursor of the same material may be multilayered before the final heat treatment. Covering the outer surface of the composite. As another manufacturing method, the carbon material may be preliminarily mixed on the graphite material, and after the metal is mixed and then heat treated, the metal may be embedded or coated on the graphite material, and a method of mixing and reheating, etc. At this time, as a method of adhering the organic compound of the metal in the gas phase to the graphite material, the temperature of the 312XP/invention specification (supplement)/93-12/93129041 is not full, preferably the appropriate B does not soften, the local is through the powder. In addition, the operation of the state of the soft state. Unlike the device that is easy to match with the use of scale graphite, can be GRA MACHINE dragon (share) system) Nara Machinery Manufacturing Co., Ltd. (made by the Dragon Co., Ltd.) or the precursor of the heterogeneous carbon. Alternatively, the carbon material may be a PVD (Physical Vapor Deposition) method such as a vacuum 19 125888 deposition method, a mineralization method, an ion ore method, an ion ray epitaxy method, or the like, or A CVD method such as a normal pressure CVD (Chemical Vapor Deposition) method, a reduced pressure CVD method, a plasma CVD method, an MO ( Magneto-optic) CVD method, or a photo CVD method. Further, in the case of using flaky graphite, the flaky graphite may be spheroidized in advance, and then a liquid mixture of a precursor of a carbon material and a metal may be injected into the pores to mix the precursors of the carbon material. And heat treatment methods, etc. Further, in the case of using fibrous graphite, a method in which the metal and the fibrous graphite are previously integrated, and the precursor of the carbon material is mixed and heat-treated may be employed. The flaky graphite may coexist in the integration of the metal with the fibrous graphite or the subsequent heat treatment. As a method of integrating the metal with the fibrous graphite, a mechano-chemical treatment for imparting mechanical energy such as compression, shearing, impact, friction, or the like may be employed, or the metal particles may be put into the dispersed fiber. After the organic solvent of the graphite material is removed, the organic solvent is removed. When a negative electrode material or a negative electrode is produced by using the composite particles of the present invention, a commonly used conductive material, a modified material, an additive, or the like may be coexisted in the production of the negative electrode material. For example, various graphite materials such as natural graphite, artificial graphite, mesophase fired graphite compound, mesophase fibrous graphite compound, and the like, carbon materials such as amorphous hard carbon (hardcarb ο η ), carbon black or gas phase may be added. A conductive material such as carbon fiber, an organic substance such as a phenol resin, a metal such as ruthenium, or a metal compound such as tin oxide is grown. These additions are usually made in comparison to the composite granules 20 312 ΧΡ / invention specification (supplement) / 93-12/93129041 1258883.  The total amount of 1 to 50% by mass. The present invention relates to a negative electrode material for a lithium ion secondary battery containing the above composite particles, and a lithium ion secondary battery using the negative electrode material. (Negative Electrode) The negative electrode for a lithium ion secondary battery of the present invention is produced on the basis of a normal negative electrode forming method. However, there is no limitation as long as it is a method for obtaining a chemically and electrochemically stable negative electrode. In the production of the negative electrode, a binder is preferably added to the composite particles of the present invention, and a previously prepared negative electrode mixture is used. The binder is preferably one which exhibits chemical and electrochemical stability to the electrolyte. For example, a fluorine-based resin powder such as polytetrafluoroethylene or polyvinylidene fluoride; a resin powder such as polyethylene or polyvinyl alcohol; or a carboxymethyl cellulose can be used. You can also use these together. The binder is usually used in a ratio of about 1 to 2 0 w t % of the total amount of the negative electrode mixture. More specifically, first, the composite particles of the present invention are adjusted to a desired particle size by classification or the like, and a mixture obtained by mixing with a binder is dispersed in a solvent to prepare a paste (p a s t e ) to prepare a negative electrode mixture. That is, the syrup obtained by mixing the composite particles of the present invention and the binder with a solvent such as water, isopropanol, N-mercaptopyrrolidone or dimercaptomannamine is used for known mixing. Mix the machine, mixer, kneading machine, kneader, etc.: mix and mix to prepare the paste. The paste is applied to one side or both sides of the current collector and dried to obtain a negative electrode in which the negative electrode mixture layer is uniformly and strongly adhered. The film thickness of the negative electrode mixture layer is 10 to 2 0 0 // m, preferably 2 0 to 1 0 0 " m. Further, the negative electrode of the present invention may be produced by dry-mixing the composite particles of the present invention with a resin powder such as polyethylene or polyvinyl alcohol, and hot-press molding the mold. 21 312XP/Invention Manual (Supplement)/93-12/93129041 1258883 After the negative electrode mixture layer is formed and pressed by pressing or the like, the adhesion strength between the negative electrode mixture layer and the current collector can be further improved. The shape of the current collector used for the production of the negative electrode is not particularly limited. Preferred are foils, meshes, and the like. The mesh type may be an expanded metal or the like. The material of the current collector is preferably copper, non-recorded steel, and recorded. The thickness of the current collector is preferably about 5 to 2 0 // m in the case of a foil. Further, the negative electrode of the present invention may further contain a graphite material such as natural graphite or a carbon material such as amorphous hard carbon, or a phenol resin, in a composite particle containing a metal which can be alloyed with lithium, a graphite material and a carbon material. Organic compounds, metals such as ruthenium, metal compounds such as tin oxide, and the like. (Li-ion secondary battery) A lithium ion secondary battery generally has a negative electrode, a positive electrode, and a non-aqueous electrolyte as main battery constituent elements. Since the positive electrode and the negative electrode each become a carrier of lithium ions, they become a battery mechanism in which lithium ions are occluded in the negative electrode during charging and are detached from the negative electrode during discharge. The lithium ion secondary battery of the present invention is not particularly limited as long as the negative electrode material of the present invention is used as a negative electrode material, and other battery constituent elements such as a positive electrode, an electrolyte, and a separator are elements of a general lithium ion secondary battery. Prevail. (Positive Electrode) The positive electrode is formed by applying a positive electrode mixture composed of, for example, a positive electrode material and a binder and a conductive agent to the surface of the current collector. The material of the positive electrode (positive electrode active material) is preferably selected to be capable of occluding/disengaging a sufficient amount of lithium, and is: 22 312XP/invention specification (supplement)/93-12/93129041 1258883 containing transition metal oxides, transition a metal chalcogenide (cha 1 c 〇ge η ) compound, a ruthenium oxide and a compound thereof, and a compound of the formula MxM〇6S8-Y (wherein Μ is at least one transition metal element, X is 0SX) S4, Y is a value of the range of 0SYS1), a Scherrer phase compound, activated carbon, activated carbon fiber, or the like. ί凡 oxide is represented by V 2 0 5, V 6 0 1 3, V2〇4, V3〇8. The transition metal oxide containing lithium is a composite oxide of lithium and a transition metal, and may be one in which lithium and two or more kinds of transition metals are solid-solved. The composite oxide may be used singly or in combination of two or more types. The lithium-containing transition metal oxide 'specifically, is L i Μ 1 1 - X Μ 2 X 0 2 (wherein Μ 1, Μ 2 is at least one transition metal element, and X is a value in the range of 0 SXS 1) Or L i Μ 12 - γ Μ 2 γ 0 4 (wherein Μ 1, Μ 2 is a transition metal element of at least one type, and Υ is a value in the range of 0$ Υ $2). The transition metal elements represented by Μ1 and Μ2 are Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn, etc., preferably Co, Fe, Μη, Ti, Cr, V, A 1 and so on. Preferred specific examples are LiCo〇2, LiNi〇2, LiMn〇2, LiNio. 9Coo. 1O2, LiNio. 5Mno. 5O2 and so on. The lithium-containing transition metal oxide may be, for example, lithium, a transition metal oxide, a hydroxide, a salt or the like as a starting material, and the starting materials are mixed according to the composition of the desired metal oxide, in oxygen. It is obtained by firing at a temperature of 600 to 1 0 0 °C in an environment. As the positive electrode active material, the above compounds may be used singly or in combination of two or more kinds. For example, a carbonate such as lithium carbonate can be added to the positive electrode. Further, in the case of forming the positive electrode, various additives such as a conductive agent or a bonding agent which are conventionally known can be suitably used, and the like, 23 312 XP/invention specification (supplement)/93-12/93129041 1258883. In the production of the positive electrode, a positive electrode mixture composed of the above-mentioned positive electrode material, a binder, and a conductive agent for imparting conductivity to the positive electrode is applied to both surfaces of the current collector to form a positive electrode mixture layer. The binder can be used in the same manner as used in the production of the negative electrode. As the conductive agent, a known person such as graphitized product or carbon black can be used. The shape of the current collector is not particularly limited, and a mesh such as a foil or a mesh or a metal may be used. The material of the current collector is aluminum, stainless steel, nickel, and the like. It is preferred that the thickness is 10 to 40//m. The positive electrode is the same as the negative electrode, and the positive electrode mixture can be dispersed in a solvent to form a paste. The paste-like positive electrode mixture is applied to a current collector and dried to form a positive electrode mixture layer, or a positive electrode mixture can be formed. After the agent layer, pressure bonding is performed by press-pressing or the like. Thereby, the positive electrode mixture layer can be homogenized and strongly bonded to the current collector. (Non-aqueous electrolyte) The non-aqueous electrolyte used in the lithium ion secondary battery of the present invention is an electrolyte salt which is usually used for a non-aqueous electrolyte, and for example, L i P F 6 , Li b F 4 , L1 AsF6 , LiClO can be used.  , LiBCCeHs), LiCl, LiBr, LiCFaSOa, LiCHsSCh, LiN(CF3S〇2)2, LiC(CF3S〇2)" LiN(CF3CH2〇S〇2)2, LiN(CFsCF2〇S〇2)2, L i N ( HCF 2 CF 2 CH 2 0 S 0 2) 2 ,

LiN((CF3)2CHOS〇2)2、 LiB[C6H3(CF3)2]4、 LiAlCl4、 LiSiFe 等之鋰鹽。尤其是LiPFe、LiBh自氧化安定性之觀點而言 較適合使用。 電解質中之電解質鹽濃度，以 （L 1〜5 in ο 1 / 1 較佳， 24 312XP/發明說明書(補件)/93-12/93129041 1258883 Ο . 5 〜3 . 0 m ο 1 / 1 更佳。 用以作為非水電解質液之溶劑，可使用碳酸乙烯酯、碳 酸丙烯酯、碳酸二曱酯、碳酸二乙酯等之碳酸酯；1，1 -或 1,2 -二曱氧乙烷' 1,2 -二乙氧乙烷、四氫呋喃、2 -曱基四 氫呋喃、7 - 丁内酯、1，3 -二氧戊環、4 -曱基-1，3 -二氧戊 環、苯曱醚、二***等之醚；環丁砜、曱基環丁砜等之硫 醚；丙烯腈、氣化腈、丙基腈等之腈；三曱基溴酸、四曱 基矽酸、硝基甲烷、二曱基磺醯胺、N -甲基吡咯酮、醋酸 乙酯、三曱基正曱酸鹽、硝基苯、氯化苯醯、溴化苯醯、 四氫噻吩、二曱亞砜、3 -曱基-2 -噁唑酮、乙二醇、二曱硫 醚等之非質子性有機溶劑。 以高分子固體電解質、高分子膠體電解質等之高分子電 解質作為非水電解質之情況，係使用經可塑劑（非水電解 液）膠體化之高分子化合物作為基質（m a t r i X )。該基質高 分子化合物可單獨或混合使用聚環氧乙烯或其交聯體等之 醚系樹脂；聚曱基丙烯酸酯系樹脂；聚丙烯酸酯系樹脂； 聚偏二氟乙烯（PVDF)或偏氟乙烯-六氟丙烯共聚合體等之 氟系樹脂等。 此等之中，自氧化還原安定性之觀點而言，以使用聚偏 氟乙烯或偏氟乙烯-六氟丙烯共聚合體等之氟系樹脂為佳。 所使用之可塑劑可使用上述之電解質鹽或非水溶劑。於 高分子膠體電解質之情況，屬可塑劑之非水電解液中之電 解質鹽濃度以0 · 1〜5 m ο 1 / 1為佳，0 · 5〜2 · 0 m ο 1 / 1更佳。 高分子電解質之製作並無特別的限制，可列舉如：將構 25 312XP/發明說明書(補件)/93-12/93129041 1258883 成基質之高分子化合物、鋰鹽及非水溶劑（可塑劑）等予 以混合，並加熱而熔融·溶解高分子化合物之方法；於混 合用有機溶劑中使高分子化合物、鋰鹽、以及非水溶劑溶 解後，使混合用有機溶劑蒸發之方法；將聚合性單體、鋰 鹽以及非水溶劑混合，對混合物照射紫外線、電子束或分 子射線等，使聚合性單體聚合而得到高分子化合物之方法 等。 高分子電解質中之非水溶劑之比例以 1 0〜9 0質量％為 佳，3 0〜8 0質量％更佳。若未滿1 0質量％，則導電率變低， 而若超過9 0質量％ ，則機械強度變弱，不易成膜化。 (分隔片） 本發明之鋰離子二次電池中，亦可使用分隔片。分隔片 之材質或構造並無特別限制，可列舉如織布、不織布、合 成樹脂製微多孔膜等。以合成樹脂製微多孔膜較為合適， 其中又以聚烯烴系微多孔膜在厚度、膜強度、膜電阻等方 面較適合。具體而言為聚乙烯及聚丙烯製微多孔膜或將該 等複合之微多孔膜等。 本發明之鋰離子二次電池中，由於使用端面未露出之中 間相小球體作為負極用碳材料，因此亦可使用膠體電解質。 使用膠體電解質之鋰離子二次電池，係由含有上述複合 粒子之負極、正極以及膠體電解質所構成。例如，可藉由 以負極、膠體電解質、正極之順序層合，並收藏於電池外 包裝材内而製作。另外，除此之外，亦可進一步於負極與 正極之外側摻配膠體電解質。 26 312XP/發明說明書(補件)/93-〗2/93129041 1258883 此外，本發明之鋰離子二次電池之構造係為任意，對於 其形狀、形態並無特別的限制，可視用途、搭載機器、所 要求之充放電容量等，自圓筒型、方型、硬幣型、鈕釦型 等之中任意選擇。為了得到安全性更高之密閉型非水電解 液電池，最好具備在過充電等異常時感測電池内壓上升並 阻斷電流之手段。於高分子固體電解質電池或高分子膠體 電解質電池之情況，亦可作成封入有層合膜之構造。 (實施例） 其次，藉由實施例及比較例更具體地說明本發明，但本 發明並不限定於此等例子。又，於實施例及比較例中，製 作圖1所示之構成的評估用鈕釦型二次電池並進行評估。 實體電池可以本發明之目的為基礎，根據周知之方法而製 作。於該評估用電池中，作用極係表現為負極，對極係表 現為正極。 於實施例及比較例中，碳材料之先質的殘碳率係以 J I S K 2 4 2 5之固定碳法為基準，以如下方式測定。 量取g之碳材料於坩鍋中，在無蓋之狀態下於4 3 0 °C之 電爐中加熱3 0分鐘。之後，作成二重坩鍋，於8 0 0 °C之電 爐中加熱3 0分鐘，除去揮發份，將殘餘份量之百分率作為 殘碳率。 複合粒子之平均粒徑係使用雷射繞射式粒度分佈計（歇 易欣公司製，L S - 5 0 0 0 )而測定，將累積度數以體積分率計 成為5 0 %的粒徑設為平均粒徑。 複合粒子整體之孔隙度係使用水銀孔隙度儀測定總孔隙 27 312XP/發明說明書(補件)/93-12/93129041 1258883 之容積，求出相對於複合粒子整體容積之比例。 比表面積係以氮氣吸附之B E T法求得。 X射線繞射之晶格面間隔d〇2係以上述方法測定。 相對於複合粒子之總孔隙之該金屬周圍之孔隙的比 係藉由計算粒子剖面之掃瞄式電子顯微鏡觀察的二維 區域面積比例而求出，採用5 0個複合粒子之剖面的計 果之平均值。其中，孔隙若直接接觸該金屬表面之至 部份而存在，則為該金屬周圍之孔隙。 另外，於複合粒子中之該金屬的比例係以上述之發 光法而求出。石墨材料與碳材料之比例係以使用上述 光顯微鏡的方法求得。 又，拉曼分光之 R值係使用雷射拉曼分光分析 (N R - 1 8 0 0，日本分光（股）製），以激發光為5 1 4 · 5 ] 氬離子雷射、照射面積為5 0 // m p之條件進行分析，為 帶域1 3 6 0 c ηΓ 1波峰強度為I D、G帶域1 5 8 0 c ιιΓ 1波峰強 I G時之比I D / I G。 (實施例1 ) (複合粒子之製造） 將於酚樹脂（住友貝庫萊特（股）製，殘碳率5 0 % 乙醇溶液中分散有金屬矽粉末（高純度化學研究所（ 製，平均粒徑 2 // m )之糊漿、與天然石墨（（股）中 墨工業所製，平均粒徑1 0 // m )，使用雙軸加熱捏合機 1 5 0 °C下混練1小時，得到混練物。此時，調製成固形 質量百分率為酚樹脂1 8 w t %、矽粉末6 w t %、天然石墨 312XP/發明說明書(補件)/93-12/93129041 例， 孔隙 測結 少一 光分 之偏 裝置 1Π1之 令D 度為 )之 股） 越石 ，於 份之 7 6 w t 28 1258883 % 。另外，本案之固形份係表示調製溶液前之常溫下之固 體狀態之物質。 其次，於煤炭焦油瀝青（杰富意化學（股）製，殘碳率 6 0 % )中混合焦油中油，調製煤炭焦油瀝青溶液。使用雙 軸加熱捏合機，將該溶液與該混練物於2 0 0 °C下混練1小 時。此時，調製成固形份之質量百分率為煤炭焦油瀝青 3 0 w t %、該混練物7 0 w t %。混練後，使之呈真空而除去該 混練物中之溶劑。 將所得之混練物予以粗粉碎之後，於 1 0 0 0 °C下加熱 1 0 小時，將該混練物作成實質上不含揮發物之狀態。亦即， 使酚樹脂及煤炭焦油瀝青碳化。所得之複合粒子之平均粒 徑為 1 5 # m。測定所得之複合粒子中各構成材料之質量百 分率、複合粒子整體之孔隙度、以及相對於複合粒子之總 孔隙之金屬周圍的孔隙比例等，將結果示於表 1 - 1 及表 1 -2 ° 又，針對複合粒子之剖面，使用掃瞄式電子顯微鏡以觀 察粒子内之構造。結果以示意圖之方式示於圖 2。如此可 知，可與鋰合金化之金屬矽1 2之至少一部份，係接觸於石 墨材料1 1及/或碳材料1 3，且該金屬之周圍之孔隙亦接觸 於該金屬1 2之表面的至少一部份。另外，元件符號1 4係 石墨材料之邊緣面，且元件符號1 5係石墨材料之基礎面。 (負極混合劑糊之製作） 將 9 0 w t %之上述複合粒子與 1 0 w t %之聚偏二氟乙烯放 入N -曱基吡咯酮中，使用均質攪拌器，以2 0 0 0 r p m攪拌混 29 312XP/發明說明書(補件)/93-12/93129041 1258883 合3 0分鐘，調製有機溶劑系負極混合劑。 (作用電極（負極）之製作） 將上述負極混合劑糊以均勻的厚度塗佈於銅箔，於真空 中9 0 °C下使溶劑揮發並乾燥，以手壓機對負極混合劑層加 壓。將銅箔與負極混合劑層打錠為直徑1 5 . 5 m m之圓柱狀， 製作由集電體、密著於該集電體之負極混合劑所構成之作 用電極（負極）。 (對極之製作） 將鋰金屬箔按壓於鎳網，打錠為直徑1 5 . 5 m m之圓柱狀， 製作由鎳網所構成之集電體與密著於該集電體之鋰金屬箔 所構成之對極。 (電解液•分隔片） 於混合有3 3 v ο 1 %之碳酸乙烯酯、6 7 v ο 1 %之碳酸甲乙酯 之溶劑中，溶解L i P F 6使其濃度成為1 m ο 1 / d m3，調製非水 電解液。將所得之非水電解液含浸於聚丙烯多孔質體，製 作含浸有電解液之分隔片。 (評估電池） 製作圖1所示之鈕釦型二次電池，作為評估電池。 在密著於集電體7b之負極2、密著於集電體7a之正極4 之間，夾入含浸有電解液之分隔片 5，予以積層。之後， 以負極集電體7b側收藏於外包裝杯狀殼1内、且正極集電 體7 a側收藏於外包裝罐3内之方式，對齊外包裝杯狀殼1 與外包裝罐3。此時，在外包裝杯狀殼1與外包裝罐3之 周緣部，使絕緣填塞物6介存於其間，使兩周緣部摺皺而 30 312XP/發明說明書(補件)/93-12/93129〇41 1258883 密封。 針對該評估電池，於溫度 2 5 °C下進行下述之充放電試 驗，計算放電容量、初期充放電效率、循環特性。將評估 結果示於表2。 (放電容量•初期充放電效率） 以0 . 9 m A之電流值進行定電流充電，直至電路電壓達到 OmV為止，並於電路電壓達到OmV時切換為定電壓充電， 再繼續充電至電流值成為2 0 // A為止。從其間之通電量求 出充電容量。之後，休息1 2 0分鐘。其次，以0. 9 m A之電 流值進行電流放電，直至電路電壓達到1 . 5 V為止，並從其 間之通電量求出放電容量。由下式計算初期充放電效率。 另外，此試驗中，將鋰對石墨質粒子吸留之過程定為充電， 脫離之過程定為放電。 初期充放電效率（％ )=(第1循環之放電容量/第1循環之充電容量）xl 00 (循環特性） 以4 . 0 m A之電流值進行定電流充電至電路電壓達到0 m V 為止之後，切換為定電壓充電，繼續充電至電流值成為20 // A為止後，休息1 2 0分鐘。其次，以4. 0 m A之電流值進 行定電流放電，直至電路電壓達到1 . 5 V為止。反覆充放電 2 ◦次。利用下式計算循環特性。 循環特性=(第20循環之放電容量/第1循環之放電容量）xl 00 電池特性（放電容量、初期充放電效率及循環特性）之 評估結果示於表2。 如表2所示，使用實施例1之複合粒子於作用電極中所 31 312XP/發明說明書(補件)/93-12/93129041 1258883 得之評估電池，顯示出高的放電容量，且具有高的初期充 放電效率。此外，顯示優異的循環特性。 (實施例2 ) 於實施例1中，在使用雙軸加熱捏合機於1 5 0 °C下將天 然石墨與使金屬矽粉末分散於酚樹脂之乙醇溶液而成之糊 漿混練1小時之際，係調製為固形份之質量百分率為酚樹 脂2 0 . 4 w t %、矽粉末6 . 7 w t %、天然石墨7 2 · 9 w t %，得到 混練物。又，其次，使用雙軸加熱捏合機將煤炭焦油遞青 溶液與該混練物於2 0 0 °C下混練 1小時之際，係調製為固 形份之質量百分率為煤炭焦油瀝青 3 6 . 9 w t % 、該混練物 6 3 . 1 w t % 。除此之外，以與實施例1同樣的方法與條件， 製作複合粒子。接著，與實施例1同樣地，製作負極混合 劑糊、作用電極、對極、電解液•分隔片及評估電池。測 定該評估電池之充放電特性。 (實施例3 ) 於實施例1中，除了取代鱗片狀之天然石墨，改用將塊 狀焦炭石墨化之人造石墨（平均粒徑為 1 0 // m )之外，以 與實施例1同樣的方法與條件，製作複合粒子。接著，與 實施例1同樣地，製作負極混合劑糊、作用電極、對極、 電解液•分隔片及評估電池。測定該評估電池之充放電特 性。 (實施例4 ) 將經石墨化處理之氣相成長碳纖維（昭和電工（股）製， V G C F，短軸長1 5 0 n m，平均縱橫比約5 0 ) 9 2 „ 7 w t %、與矽 32 312XP/發明說明書(補件)/93-12/93129041 1258883 粒子（高純度化學研究所（股）製，平均粒徑2 // m ) 7 · 3 w t %混合，置入於機械鬲i合系統 (mechanofusion system， 細川米克龍（股）製）中，賦予機械性能量，施以機械化 學處理。亦即，以旋轉鼓之圓周速度2 0 m / s、處理時間3 0 分鐘、旋轉鼓與内部構件之距離5 m m之條件反覆附加剪切 力，得到石夕粒子被包炎於氣相成長碳纖維之複合粒子。 其次，使用雙軸加熱捏合機，將於煤炭焦油遞青（杰富 意化學（股）製，殘碳率6 0 % ) 3 0 g中混合有焦油中油（杰 富意化學（股）製）3 0 0 g調製而成之煤炭焦油瀝青溶液、 與該複合粒子，於2 0 0 °C下混練 1小時。此時，調製成固 形份之質量百分率為煤炭焦油瀝青 4 2 w t % 、該複合粒子 5 8 w t %。混練後，使之成真空，將溶劑焦油中油自該混練 物中除去，得到被覆有煤炭焦油瀝青之複合粒子。將所得 之複合粒子粗粉碎後，於1 0 0 0 °C下燒製1 0小時，得到被 覆複合粒子。於燒製之際，揮發份實質上被完全去除。以 該碳材料被覆之複合粒子為球狀，平均粒徑為 1 0 // m，比 表面積為5.2m2/g。 該碳材料係被覆於該複合粒子之外表面，矽粒子被絡合 包夾於氣相成長碳纖維中，且大量的孔隙分散形成於複合 粒子的内部整體，已得到確認。所得之被覆複合粒子之構 成成分之質量百分率為石夕5 β 1 w t %、纖維狀石墨材料6 4 . 6 w t %、碳材料 3 0 . 3 w t %。 接著，與實施例1同樣地，製作負極混合劑糊、作用電 極、對極、電解液•分隔片及評估電池。測定該評估電池 33 312XP/發明說明書(補件)/93-12/93129041 1258883 之充放電特性。 (實施例5 ) 於實施例1中，在使用雙軸加熱捏合機將煤炭焦油 與石墨材料、碳材料於 2 0 0 °C下混練 1小時之際，加 片狀天然石墨（（股）中越石墨工業所製，平均粒徑5 β 調整固形份之質量百分率成為煤炭焦油瀝青3 4 w t %、 粒子 6 0 w t % 、天然石墨 6 w t %。除此之外，以與實施 同樣的方法與條件製作複合粒子，接著進行燒製，得 覆複合粒子。所得之被覆複合粒子為塊狀’平均粒徑 //in5比表面積為5.3m2/g。 該碳材料被覆於該複合粒子之外表面，矽粒子係絡 夾於氣相成長碳纖維中，其周圍配置有天然石墨，且 的孔隙分散形成於複合粒子的内部整體，已得到確認 得之被覆複合粒子之構成成分之質量百分率為矽 5 %、纖維狀石墨材料6 4 . 8 w t %、鱗片狀石墨材料6 . 5 w 碳材料2 3 . 6 w t %。 接著，與實施例1同樣地，製作負極混合劑糊、作 極、對極、電解液•分隔片及評估電池。測定該評估 之充放電特性。 (實施例6 ) 於實施例4中，在使用雙軸加熱捏合機將煤炭焦油 溶液與複合粒子於 2 0 0 °C下混練1小時之際，除了調 形份之質量百分率成為煤炭焦油瀝青 1 0 w t % 、複合 9 0 w t %之外，以與實施例3同樣的方法與條件，製作 312XP/發明說明書(補件)/93-12/93129041 渥青 入鱗 m )， 複合 例1 到被 為1 2 合包 大量 〇所 .1 w t t%、 用電 電池 遞青 整固 粒子 複合 34 製作負極混合劑糊、作用電 評估電池。測定該評估電池 ，使用錫粉末（A 1 d r i c h製， 乙醇溶液中與天然石墨混合 率成為酚樹脂1 8 w t %、錫粉 t%。除此之外，以與實施例 粒子。接著，與實施例 1同 用電極、對極、電解液•分 電池之充放電特性。 將矽粉末粉碎並製成平均粒 實施例1同樣的方法與條件 例1同樣地，製作負極混合 液•分隔片及評估電池。測 為分散媒、並以珠磨將石夕粉 m者。除此之外，以與實施例 粒子。由X射線繞射測定， 。接著，與實施例1同樣地， 、對極、電解液•分隔片及 1258883 粒子。 接著，與實施例1同樣地， 極、對極、電解液•分隔片及 之充放電特性。 (實施例7 ) 於實施例1中，取代矽粉末 平均粒徑 1 // m )，在酚樹脂之 之際，調整固形份之質量百分 末26.7wt%、天然石墨55,3w 1同樣的方法與條件製作複合 樣地，製作負極混合劑糊、作 隔片及評估電池。測定該評估 (實施例8 ) 於實施例1中，使用以球磨 徑0 . 5 m者。除此之外，以與 製作複合粒子。接著，與實施 劑糊、作用電極、對極、電解 定該評估電池之充放電特性。 (實施例9 ) 於實施例1中，使用以水作 末粉碎並製成平均粒徑（K 3 // 1同樣的方法與條件製作複合 確認經粉碎的矽粉末為非晶質 製作負極混合劑糊、作用電極 312XP/發明說明書(補件)/93-12/93129041 35 1258883 評估電池。測定該評估電池之充放電特性。 (比較例1 ) 將實施例1中所使用之金屬矽粉末、鱗片狀之天然石墨 以及煤炭焦油瀝青之固形份之質量百分率，分別調製成為 3 . 8 w t %、3 8 . 5 w t %、5 7 . 7 w t %，以焦油中油作為溶劑，同 時以雙軸加熱捏合機混練後，加熱混練物，除去溶劑，並 予以乾燥。將所得之混練物粉碎，於1 0 0 0 °C下燒製1 0小 時，製作複合粒子。接著，以與實施例1同樣的方法與條 件，使用該複合粒子、負極以及非水電解質，製作鋰離子 二次電池。與實施例1同樣地測定該電池之放電容量、初 期充放電效率與循環特性，將評估結果示於表2。 (比較例2 ) 於比較例1中，將金屬矽粉末、鱗片狀之天然石墨、以 及煤炭焦油瀝青之固形份之質量百分率分別調製成為 3 · 7 w t %、3 3 . 8 w t %、6 2 · 5 w t %。除此之外，以與比較例1 同樣的方法與條件製作複合粒子。接著，以與實施例1同 樣的方法與條件，使用該複合粒子、負極以及非水電解質， 製作鋰離子二次電池。與實施例1同樣地測定該電池之放 電容量、初期充放電效率與循環特性，將評估結果示於表 2。 在矽粒子的周圍未存在有孔隙的比較例1、2中，無法得 到高的初期充放電效率與循環特性。此原因可能為因充電 時的矽粒子之膨脹，破壞複合粒子的構造，導致導電性之 降低與活性物質自集電體之剝離產生。 36 312XP/發明說明書(補件)/93-12/93129041 1258883 表 1 _ 1 複棘子猶減分與滅 金屬 石墨材♦ 碳材料 麵 平均粒徑 (_) (wt%) 麵 (wt%) 先質之種類 滅 (wt%) 侧列1 結晶碎 2 5.1 鱗片狀天然石墨 65.1 獅封脂 煤炭焦油瀝青 29.8 倾例2 結晶珍 2 5.1 鱗片狀天然石墨 55.1 _脂 煤炭焦油瀝青 39.8 雜例3 結晶珍 2 5.1 塊狀人造石墨 65.1 義脂 煤炭焦油瀝青 29.8 WM 結晶碎 2 5.1 孅維狀^墨 64.6 煤炭焦油遞青 30.3 侧列5 結晶碎 2 5.1 纖維狀^墨 鱗片狀天然^墨 64.8 6.5 煤炭焦油遞青 23.6 雜例6 結晶碎 2 6.8 纖维狀^墨 86.9 煤炭焦油瀝青 6.3 細列7 結晶錫 1 23 鱗片狀天然^墨 47.2 封月旨 煤炭焦油瀝青 29.8 雜例8 結晶珍 0.5 5.1 鱗片狀天然^墨 65.1 娜i脂 煤炭焦油瀝青 29.8 細列9 非副·生石夕 0.3 5.1 鱗片狀天然石墨 65.1 賴脂 煤炭焦油瀝青 29.8 bt|交例1 結晶碎 2 5 鱗片狀天然^墨 50 煤炭焦油渥青 45 mm2 結晶碎 2 5 鱗片狀天然石墨 45 煤炭焦油瀝青 50 1-2 表 複棘子之謝生 平均粒徑 (#m) 面積 (m2/g) 拉曼分光 (R值） 鏹之孔敝 (%) 該金屬周圍之孔隙度 (%) 晶格面間隔 (nm) 細列1 15 4 0.29 25 55 - 細列2 15 5 0.28 22 25 - 細列3 13 5 0.45 26 58 一 例4 10 14 0.3 30 64 0.3366 ^包例5 12 9 0.35 33 60 0.3366 雜例6 10 23 0.32 32 55 0.3366 15 4 0.29 25 55 一 實施例8 13 6 0.3 28 48 - 獅列9 14 7 0.31 31 50 - _歹丨J1 15 5 0.32 30 15 - _例2 15 5 0.34 32 10 - 37 312XP/發明說明書(補件)/93-12/93129041 1258883 表 放電容量（mAh/g) 初期充放電效率（％) 循環特性（％) 實施例1 487 87 90 實施例2 485 86 88 實施例3 480 88 87 實施例4 477 90 93 實施例5 480 92 94 實施例6 478 88 87 實施例7 486 87 87 實施例8 487 88 91 實施例9 487 87 92 比較例1 475 84 76 比較例2 474 83 72 使用含有本發明之複合粒子之負極材料於負極之鋰離 子二次電池，其放電容量大，初期充放電效率以及循環特 性優異。因此，使用本發明之負極材料所構成的鋰離子二 次電池，可滿足近年來對於高能量密度化之期望，對於搭 載之機器的小型化及高性能化有其效果。又，本發明之複 合粒子可使用向來被使用作為複合粒子之材料作為其材料 而製造，因此材料之取得容易，具有材料成本低廉之優點。 【圖式簡單說明】 圖1係顯示用以使用於充放電試驗之鈕釦型評估電池之 構造之示意剖面圖。 圖2係例示於實施例1之複合粒子之剖面示意圖。 【主要元件符號說明】 1 外包裝杯狀殼 2 負極 3 外包裝罐 4 正極 38 312XP/發明說明書(補件)/93- ] 2/93129041 1258883LiN ((CF3)2CHOS〇2)2, lithium salt of LiB[C6H3(CF3)2]4, LiAlCl4, LiSiFe or the like. In particular, LiPFe and LiBh are more suitable for use from the viewpoint of oxidation stability. The concentration of the electrolyte salt in the electrolyte is (L 1~5 in ο 1 / 1 is preferred, 24 312XP / invention specification (supplement) / 93-12/93129041 1258883 Ο . 5 ~ 3. 0 m ο 1 / 1 For use as a solvent for the nonaqueous electrolyte solution, a carbonate such as ethylene carbonate, propylene carbonate, dinonyl carbonate or diethyl carbonate; 1,1 - or 1,2 -dimethoxyethane can be used. ' 1,2-diethoxyethane, tetrahydrofuran, 2-indenyltetrahydrofuran, 7-butyrolactone, 1,3 -dioxolane, 4-mercapto-1,3-dioxolane, benzoquinone Ether of ether, diethyl ether, etc.; thioether of sulfolane, decyl sulfolane, etc.; nitrile of acrylonitrile, gasified nitrile, propyl nitrile, etc.; tridecyl bromic acid, tetradecanoic acid, nitromethane, diterpene Sulfosamine, N-methylpyrrolidone, ethyl acetate, trimethylsulfonate, nitrobenzene, phenylhydrazine chloride, phenylhydrazine bromide, tetrahydrothiophene, disulfoxide, 3 -曱An aprotic organic solvent such as oxazolone, ethylene glycol or dithizone. A polymer electrolyte such as a polymer solid electrolyte or a polymer colloidal electrolyte is used as the nonaqueous electrolyte. A polymer compound which is colloidalized with a plasticizer (non-aqueous electrolyte) is used as a matrix (matri X). The matrix polymer compound may be used alone or in combination with an ether resin such as polyethylene oxide or a crosslinked body thereof; A acrylate-based resin; a polyacrylate-based resin; a fluorine-based resin such as a polyvinylidene fluoride (PVDF) or a vinylidene fluoride-hexafluoropropylene copolymer, etc. Among these, from the viewpoint of oxidation-reduction stability In other words, a fluorine-based resin such as polyvinylidene fluoride or a vinylidene fluoride-hexafluoropropylene copolymer is preferably used. The above-mentioned electrolyte salt or non-aqueous solvent can be used as the plasticizer to be used. In the case of a polymer colloidal electrolyte, The concentration of the electrolyte salt in the non-aqueous electrolyte which is a plasticizer is preferably 0. 1 to 5 m ο 1 / 1 , and more preferably 0 · 5 to 2 · 0 m ο 1 / 1. The production of the polymer electrolyte is not particularly special. The limitation is, for example, mixing a polymer compound, a lithium salt, a non-aqueous solvent (plasticizer), etc., into a matrix, and heating and melting the composition 25 312XP/invention specification (supplement)/93-12/93129041 1258883. ·Soluble polymer compound a method of dissolving a polymer compound, a lithium salt, and a nonaqueous solvent in an organic solvent for mixing, and evaporating the organic solvent for mixing; and mixing the polymerizable monomer, the lithium salt, and the nonaqueous solvent to irradiate the mixture A method of obtaining a polymer compound by polymerizing a polymerizable monomer such as an ultraviolet ray, an electron beam or a molecular ray, etc. The ratio of the nonaqueous solvent in the polymer electrolyte is preferably 10 to 90% by mass, and 30 to 80%. When the mass % is more than 10% by mass, the electrical conductivity is low, and if it exceeds 90% by mass, the mechanical strength is weak and the film formation is difficult. (Separator) A separator may be used in the lithium ion secondary battery of the present invention. The material or structure of the separator is not particularly limited, and examples thereof include a woven fabric, a non-woven fabric, and a synthetic resin microporous film. A microporous film made of a synthetic resin is suitable, and among them, a polyolefin-based microporous film is suitable in terms of thickness, film strength, film resistance and the like. Specifically, it is a microporous film made of polyethylene or polypropylene, or a microporous film or the like which is composited. In the lithium ion secondary battery of the present invention, since the intermediate phase small sphere is not exposed as the carbon material for the negative electrode, a colloidal electrolyte can also be used. A lithium ion secondary battery using a colloidal electrolyte is composed of a negative electrode containing the above composite particles, a positive electrode, and a colloidal electrolyte. For example, it can be produced by laminating in the order of a negative electrode, a colloidal electrolyte, and a positive electrode, and collecting it in a battery outer packaging material. Further, in addition to this, a colloidal electrolyte may be further blended on the outer side of the negative electrode and the positive electrode. In addition, the structure of the lithium ion secondary battery of the present invention is arbitrary, and the shape and shape thereof are not particularly limited, and it is possible to use the device, the use device, and the like. The required charge and discharge capacity and the like are arbitrarily selected from a cylindrical type, a square type, a coin type, and a button type. In order to obtain a safe non-aqueous electrolyte battery, it is preferable to have a means for sensing an increase in the internal pressure of the battery and blocking the current when an abnormality such as overcharge occurs. In the case of a polymer solid electrolyte battery or a polymer colloidal electrolyte battery, a structure in which a laminated film is sealed may be used. (Embodiment) Next, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto. Further, in the examples and the comparative examples, the evaluation button-type secondary battery having the configuration shown in Fig. 1 was produced and evaluated. The solid battery can be made according to the purpose of the present invention, according to a known method. In the battery for evaluation, the working electrode showed a negative electrode and the opposite electrode showed a positive electrode. In the examples and the comparative examples, the carbon residue ratio of the precursor of the carbon material was measured in the following manner based on the fixed carbon method of J I S K 2 4 2 5 . The carbon material of g was weighed in a crucible, and heated in an electric furnace at 430 ° C for 30 minutes without a lid. Thereafter, a double crucible was prepared, and it was heated in an electric oven at 80 ° C for 30 minutes to remove volatiles, and the percentage of the residual amount was taken as the residual carbon ratio. The average particle diameter of the composite particles was measured using a laser diffraction type particle size distribution meter (LS-5500), and the cumulative degree was set to 50% by volume. The average particle size. The porosity of the composite particles as a whole is measured by a mercury porosimeter using the volume of the total pores 27 312 XP / invention specification (supplement) / 93-12 / 93129941 1258883, and the ratio with respect to the overall volume of the composite particles is determined. The specific surface area was determined by the B E T method of nitrogen adsorption. The lattice spacing d〇2 of the X-ray diffraction is measured by the above method. The ratio of the pores around the metal relative to the total pores of the composite particles is determined by calculating the ratio of the area of the two-dimensional region observed by the scanning electron microscope of the particle profile, and the profile of the 50 composite particles is used. average value. Where the pores are present if they are in direct contact with the portion of the metal surface, they are pores around the metal. Further, the ratio of the metal in the composite particles was determined by the above-described luminescence method. The ratio of the graphite material to the carbon material was determined by the method using the above light microscope. Further, the R value of Raman spectroscopy is measured by laser Raman spectroscopic analysis (NR - 1 800, manufactured by JASCO Corporation), with an excitation light of 5 1 4 · 5 ] argon ion laser, and an irradiation area of 5 0 // The condition of mp is analyzed as the ratio ID / IG of the band 1 3 6 0 c η Γ 1 peak intensity is ID, G band 1 5 8 0 c ιιΓ 1 peak intensity IG. (Example 1) (Production of composite particles) Metal ruthenium powder (dispersed by high-purity chemical research institute (manufactured by Sumitomo Becule), a residual carbon ratio of 50% ethanol solution The syrup of diameter 2 // m) and natural graphite (manufactured by China National Cotton Industry Co., Ltd., average particle size 10 // m) were mixed for 1 hour at 150 °C using a biaxial heating kneader. The kneaded material. At this time, the mass percentage of the solid content is 8% of the phenol resin, 6 wt% of the bismuth powder, natural graphite 312XP/invention specification (supplement)/93-12/93129041, and the aperture measurement is less than one light. The partiality of the device is 1Π1, and the D degree is the stock.) The stone is more than 7 6 wt 28 125888%. Further, the solid portion of the present invention means a substance which is in a solid state at a normal temperature before the solution is prepared. Secondly, the tar oil was mixed with coal tar pitch (Jie Fuyi Chemical Co., Ltd., residual carbon ratio of 60%) to prepare a coal tar pitch solution. This solution was kneaded with the kneaded material at 200 ° C for 1 hour using a biaxial heating kneader. At this time, the mass percentage of the solid content prepared into the solid portion was 3 0 w t % of the coal tar pitch, and the kneaded material was 70 w %. After the kneading, the solvent was removed by vacuuming to remove the solvent. The obtained kneaded product was coarsely pulverized, and then heated at 100 ° C for 10 hours to form the kneaded product in a state substantially free of volatile matter. That is, the phenol resin and the coal tar pitch are carbonized. The obtained composite particles had an average particle diameter of 15 # m. The mass percentage of each constituent material in the obtained composite particles, the porosity of the composite particles as a whole, and the proportion of pores around the metal of the total pores of the composite particles were measured, and the results are shown in Table 1-1 and Table 1-2 °. Further, for the cross section of the composite particles, a scanning electron microscope was used to observe the structure in the particles. The results are shown schematically in Figure 2. Thus, at least a portion of the metal tantalum 12 that is alloyed with lithium is in contact with the graphite material 11 and/or the carbon material 13 and the pores around the metal are also in contact with the surface of the metal 12 At least part of it. Further, the component symbol 14 is an edge face of the graphite material, and the component symbol 15 is a base face of the graphite material. (Preparation of negative electrode mixture paste) 90% by weight of the above composite particles and 10% by weight of polyvinylidene fluoride were placed in N-mercaptopyrrolone, and stirred at 200 rpm using a homomixer. Mix 29 312XP / Invention Manual (supplement) / 93-12 / 93129941 1258883 For 30 minutes, prepare an organic solvent-based negative electrode mixture. (Production of Working Electrode (Negative Electrode)) The above-mentioned negative electrode mixture paste was applied to a copper foil in a uniform thickness, and the solvent was volatilized and dried in a vacuum at 90 ° C to pressurize the negative electrode mixture layer by a hand press. . The copper foil and the negative electrode mixture layer were tableted into a cylindrical shape having a diameter of 15.5 m, and a working electrode (negative electrode) composed of a current collector and a negative electrode mixture adhering to the current collector was prepared. (Production of the opposite pole) The lithium metal foil is pressed against the nickel mesh, and the ingot is a cylindrical shape having a diameter of 15.5 mm, and a current collector composed of a nickel mesh and a lithium metal foil adhered to the current collector are produced. The opposite of the composition. (Electrolyte • Separator) Dissolve L i PF 6 to a concentration of 1 m ο 1 / in a solvent mixed with 3 3 v ο 1 % of ethylene carbonate and 6 7 v ο 1 % of ethyl methyl carbonate. d m3, modulating the non-aqueous electrolyte. The obtained nonaqueous electrolytic solution was impregnated into a porous polypropylene body to prepare a separator impregnated with an electrolytic solution. (Evaluation Battery) A button type secondary battery shown in Fig. 1 was produced as an evaluation battery. A separator 5 impregnated with an electrolytic solution is interposed between the negative electrode 2 adhering to the current collector 7b and the positive electrode 4 adhering to the current collector 7a, and laminated. Thereafter, the outer casing cup 1 and the outer can 3 are aligned so that the negative electrode current collector 7b is housed in the outer casing cup 1 and the positive electrode current collector 7a is housed in the outer can 3. At this time, in the peripheral portion of the outer casing cup 1 and the outer can 3, the insulating packing 6 is interposed therebetween, and the two peripheral portions are wrinkled. 30 312XP/Invention Manual (Supplement)/93-12/93129〇 41 1258883 Sealed. For the evaluation battery, the following charge and discharge tests were carried out at a temperature of 25 ° C to calculate the discharge capacity, initial charge and discharge efficiency, and cycle characteristics. The evaluation results are shown in Table 2. (Discharge capacity • Initial charge and discharge efficiency) Constant current charging is performed at a current value of 0.9 m A until the circuit voltage reaches 0 mV, and when the circuit voltage reaches OmV, it is switched to constant voltage charging, and then charging is continued until the current value becomes 2 0 // A so far. The charging capacity is obtained from the amount of energization therebetween. After that, rest for 120 minutes. Next, current discharge was performed at a current value of 0.99 A until the circuit voltage reached 1.5 V, and the discharge capacity was obtained from the amount of energization therebetween. The initial charge and discharge efficiency was calculated from the following formula. In addition, in this test, the process of occluding lithium into the graphite particles was determined to be charged, and the process of detachment was designated as discharge. Initial charge/discharge efficiency (%) = (discharge capacity of the first cycle / charge capacity of the first cycle) xl 00 (cycle characteristics) Constant current charging with a current value of 4.0 m A until the circuit voltage reaches 0 m V After that, switch to constant voltage charging, continue charging until the current value becomes 20 // A, and then rest for 120 minutes. Next, a constant current discharge is performed at a current value of 4.0 m A until the circuit voltage reaches 1.5 V. Repeat charging and discharging 2 times. The loop characteristics were calculated using the following formula. Cyclic characteristics = (discharge capacity at the 20th cycle / discharge capacity at the first cycle) xl 00 Battery characteristics (discharge capacity, initial charge and discharge efficiency, and cycle characteristics) The evaluation results are shown in Table 2. As shown in Table 2, the evaluation battery obtained by using the composite particles of Example 1 in the working electrode, 31 312 XP / invention specification (supplement) / 93-12/93129041 1258883, showed high discharge capacity and had high Initial charge and discharge efficiency. In addition, it exhibits excellent cycle characteristics. (Example 2) In Example 1, on the occasion of mixing a natural graphite with a paste obtained by dispersing a metal cerium powder in an ethanol solution of a phenol resin at 150 ° C for 1 hour using a biaxial heating kneader The mass percentage of the solid content is 0.02% by weight of the phenol resin, 6.7 wt% of the cerium powder, and 7 2 · 9 wt% of the natural graphite to obtain a kneaded product. Further, secondly, when the coal tar telluric solution and the kneaded product are kneaded at 200 ° C for 1 hour using a biaxial heating kneader, the mass percentage of the solid content is coal tar pitch 3 6 . 9 wt %, the kneaded material 6 3 . 1 wt %. Otherwise, composite particles were produced in the same manner and under the same conditions as in Example 1. Next, in the same manner as in Example 1, a negative electrode mixture paste, a working electrode, a counter electrode, an electrolyte solution, a separator, and an evaluation battery were prepared. The charge and discharge characteristics of the evaluation battery were measured. (Example 3) In the same manner as in Example 1, except that the scaly natural graphite was replaced with artificial graphite which graphitized the block coke (having an average particle diameter of 10 // m). The method and conditions for making composite particles. Next, in the same manner as in Example 1, a negative electrode mixture paste, a working electrode, a counter electrode, an electrolyte solution, a separator, and an evaluation battery were prepared. The charge and discharge characteristics of the evaluation battery were measured. (Example 4) A graphitized vapor-grown carbon fiber (made by Showa Denko Co., Ltd., VGCF, short axis length 150 nm, average aspect ratio about 5 0) 9 2 „ 7 wt %, and 矽32 312XP/Invention Manual (supplement)/93-12/93129041 1258883 Particles (manufactured by High Purity Chemical Research Institute, average particle size 2 // m) 7 · 3 wt % mixed, placed in mechanical 鬲i system (Mechanofusion system, manufactured by Hosokawa Mikron Co., Ltd.), mechanical energy is applied to the mechanical energy, that is, the peripheral speed of the rotating drum is 20 m / s, the processing time is 30 minutes, and the drum is rotated. The internal component is separated by a shear force of 5 mm, and the composite particles of the gas-growth carbon fiber are obtained. Next, using a biaxial heating kneader, the coal tar will be re-greened (Jie Fuyi Chemical) (share) system, residual carbon ratio of 60%) 3 0 g mixed with tar oil (Jie Fuyi Chemical Co., Ltd.) 3 0 0 g prepared coal tar pitch solution, and the composite particles, in 2 Mixing for 1 hour at 0 0 ° C. At this time, the mass percentage of the solid content is adjusted. Coal tar pitch is 4 2 wt %, and the composite particles are 58 wt%. After kneading, the mixture is vacuumed, and the solvent tar oil is removed from the kneaded material to obtain composite particles coated with coal tar pitch. After coarsely pulverizing, it was fired at 100 ° C for 10 hours to obtain coated composite particles. At the time of firing, the volatile matter was substantially completely removed. The composite particles coated with the carbon material were spherical and average. The particle size is 10 // m, and the specific surface area is 5.2 m 2 /g. The carbon material is coated on the outer surface of the composite particle, and the ruthenium particles are complexed and sandwiched in the vapor-grown carbon fiber, and a large amount of pores are dispersed. The internal mass of the composite particles has been confirmed. The mass percentage of the constituent particles of the coated composite particles obtained is Shixi 5 β 1 wt %, the fibrous graphite material 6 4 . 6 wt %, and the carbon material 3 0 . 3 wt %. Next, in the same manner as in Example 1, a negative electrode mixture paste, a working electrode, a counter electrode, an electrolyte solution, a separator, and an evaluation battery were prepared. The evaluation battery 33 312XP/invention specification (supplement)/93-12/93129041 was measured. 1258883 Discharge characteristics. (Example 5) In Example 1, when coal tar was mixed with graphite material and carbon material at 200 ° C for 1 hour using a biaxial heating kneader, flake natural graphite was added (( Manufactured by Sino-Vietnamese Graphite Industry, the mass fraction of the average particle size of 5 β adjusted solids became 3 4 wt % of coal tar pitch, 60 wt % of particles, and 6 wt % of natural graphite. In addition to this, composite particles were produced in the same manner and under the conditions of carrying out, and then fired to obtain composite particles. The obtained coated composite particles had a bulky average particle diameter of //in5 and a specific surface area of 5.3 m 2 /g. The carbon material is coated on the outer surface of the composite particle, and the ruthenium particle system is sandwiched between the vapor-grown carbon fibers, and natural graphite is disposed around the ruthenium particle system, and the pores are dispersed and formed in the entire interior of the composite particle, and the composite film has been confirmed to be coated. The mass fraction of the constituents of the particles is 矽5 %, the fibrous graphite material 64. 8 wt%, the flaky graphite material 6. 5 w carbon material 2 3 . 6 wt %. Then, in the same manner as in Example 1, a negative electrode mixture paste, a counter electrode, a counter electrode, an electrolyte solution, a separator, and an evaluation battery were produced. The charge and discharge characteristics of this evaluation were measured. (Example 6) In Example 4, when the coal tar solution and the composite particles were kneaded at 200 ° C for 1 hour using a biaxial heating kneader, the mass percentage of the shaped portion became coal tar pitch 1 In the same manner and under the same conditions as in Example 3, 312XP/invention specification (supplement)/93-12/93129041 渥 入 入 m m , , , , , , , , , , , , , , , 312 312 312 312 312 312 312 For the 1 2 package, a large amount of sputum. 1 wtt%, using a battery to refine the solid particle composite 34 to make a negative electrode mixture paste, the role of electricity evaluation battery. The evaluation battery was measured using tin powder (manufactured by A 1 drich, the mixing ratio with natural graphite in the ethanol solution was 18% by weight of phenol resin, and t% of tin powder. In addition to the particles of the example. Example 1 Charging and discharging characteristics of the same electrode, the counter electrode, and the electrolyte and the sub-cell. The crucible powder was pulverized to obtain an average particle. In the same manner as in the case of Example 1, a negative electrode mixture liquid, a separator, and an evaluation battery were prepared. The particles were measured by dispersing the medium and the bead powder was milled by the bead mill. The particles of the example were measured by X-ray diffraction. Then, in the same manner as in the first embodiment, the counter electrode and the electrolysis were carried out. Liquid, separator, and 1,258,883 particles. Next, in the same manner as in Example 1, the electrode, the counter electrode, the electrolyte and the separator, and the charge and discharge characteristics thereof. (Example 7) In Example 1, the average particle diameter of the substituted cerium powder was used. 1 / m), at the time of the phenol resin, adjust the mass fraction of the solid part by 26.7 wt%, natural graphite 55, 3w 1 to prepare a composite sample by the same method and conditions, and prepare a negative electrode mixture paste as a separator And evaluate the battery. The evaluation was carried out (Example 8). In Example 1, a ball mill diameter of 0.5 m was used. In addition to this, make composite particles with and . Next, the charge and discharge characteristics of the evaluation battery were determined with the developer paste, the working electrode, the counter electrode, and the electrolysis. (Example 9) In Example 1, a negative electrode mixture paste was prepared by pulverizing with water and preparing an average particle diameter (K 3 //1 by the same method and conditions to confirm that the pulverized cerium powder was amorphous. The working electrode 312XP/invention specification (supplement)/93-12/93129041 35 1258883 evaluated the battery. The charge and discharge characteristics of the evaluation battery were measured. (Comparative Example 1) The metal ruthenium powder used in Example 1 and scaly shape were used. The mass percentage of the solid content of the natural graphite and the coal tar pitch is adjusted to 3.8 wt %, 3 8 . 5 wt %, 5 7 . 7 wt %, and the tar oil is used as a solvent while the biaxial heating kneader is used. After kneading, the kneaded material was heated, and the solvent was removed and dried. The obtained kneaded product was pulverized and fired at 100 ° C for 10 hours to prepare composite particles. Then, in the same manner as in Example 1, A lithium ion secondary battery was produced using the composite particles, the negative electrode, and the nonaqueous electrolyte. The discharge capacity, initial charge and discharge efficiency, and cycle characteristics of the battery were measured in the same manner as in Example 1. The evaluation results are shown in Table 2. (Comparative Example 2) In Comparative Example 1, the mass percentages of the solid content of the metal cerium powder, the scaly natural graphite, and the coal tar pitch were respectively adjusted to 3 · 7 wt %, 3 3 . 8 wt %, 6 2 In addition to the above, the composite particles were produced in the same manner and under the same conditions as in Comparative Example 1. Then, using the composite particles, the negative electrode, and the nonaqueous electrolyte, lithium was produced in the same manner and under the same conditions as in Example 1. In the ion secondary battery, the discharge capacity, initial charge and discharge efficiency, and cycle characteristics of the battery were measured in the same manner as in Example 1. The evaluation results are shown in Table 2. In Comparative Examples 1 and 2 in which no pores were present around the ruthenium particles. High initial charge and discharge efficiency and cycle characteristics cannot be obtained. This may be due to the expansion of the ruthenium particles during charging, which destroys the structure of the composite particles, resulting in a decrease in conductivity and a peeling of the active material from the current collector. 36 312XP /Invention Manual (Supplement)/93-12/93129041 1258883 Table 1 _ 1 Complex thorns are still reduced and metallized graphite ♦ Carbon material surface average particle size (_) (wt%) Surface (wt%) Type (wt%) side column 1 crystallized 2 5.1 scaly natural graphite 65.1 lion sealant coal tar pitch 29.8 pour case 2 crystal Jane 2 5.1 scaly natural graphite 55.1 _ fat coal tar pitch 39.8 hybrid 3 crystal Jane 2 5.1 block Artificial graphite 65.1 liquefied coal tar pitch 29.8 WM crystallization broken 2 5.1 孅 状 ^ 6 64.6 coal tar cyan 30.3 side column 5 crystal broken 2 5.1 fibrous ^ ink scales natural ^ ink 64.8 6.5 coal tar dice 23.6 6 Crystallized crushed 2 6.8 Fibrous ink 86.9 Coal tar pitch 6.3 Fine column 7 Crystalline tin 1 23 Scale-like natural ^ ink 47.2 Sealed coal tar pitch 29.8 Miscellaneous 8 Crystal Jane 0.5 5.1 Scale-like natural ^ ink 65.1 Na Fat coal tar pitch 29.8 细列 9 Non-subsidiary shengshixi 0.3 5.1 Scale-like natural graphite 65.1 Lithium coal tar pitch 29.8 bt|Case 1 Crystallized 2 5 Scale-like natural ^50 50 Coal tar indigo 45 mm2 Crystal broken 2 5 scaly natural graphite 45 coal tar pitch 50 1-2 Xiesheng average particle size (#m) area (m2/g) Raman spectroscopy (R value) 镪 敝 敝 (%) around the metal Porosity (%) Lattice spacing (nm) Fine column 1 15 4 0.29 25 55 - Fine column 2 15 5 0.28 22 25 - Fine column 3 13 5 0.45 26 58 Example 4 10 14 0.3 30 64 0.3366 ^Package example 5 12 9 0.35 33 60 0.3366 Hybrid 6 10 23 0.32 32 55 0.3366 15 4 0.29 25 55 One example 8 13 6 0.3 28 48 - Lion column 9 14 7 0.31 31 50 - _歹丨J1 15 5 0.32 30 15 - _ Example 2 15 5 0.34 32 10 - 37 312XP/Invention Manual (Supplement)/93-12/93129041 1258883 Table Discharge Capacity (mAh/g) Initial Charge and Discharge Efficiency (%) Cycle Characteristics (%) Example 1 487 87 90 Example 2 485 86 88 Example 3 480 88 87 Example 4 477 90 93 Example 5 480 92 94 Example 6 478 88 87 Example 7 486 87 87 Example 8 487 88 91 Example 9 487 87 92 Comparative Example 1 475 84 76 Comparative Example 2 474 83 72 A lithium ion secondary battery using a negative electrode material containing the composite particles of the present invention in a negative electrode has a large discharge capacity and is excellent in initial charge and discharge efficiency and cycle characteristics. Therefore, the lithium ion secondary battery comprising the negative electrode material of the present invention can satisfy the expectation of high energy density in recent years, and has an effect on miniaturization and high performance of the loaded device. Further, the composite particles of the present invention can be produced by using a material which is conventionally used as a composite particle as a material thereof, so that the material can be easily obtained and the material cost is low. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the structure of a button type evaluation battery used for a charge and discharge test. 2 is a schematic cross-sectional view showing the composite particles of Example 1. [Main component symbol description] 1 Outer package cup case 2 Negative electrode 3 Outer packaging can 4 Positive electrode 38 312XP/Invention manual (supplement)/93- ] 2/93129041 1258883

5 分 隔 片 6 絕 緣 填 塞 物 7a 集 電 體 7b 集 電 體 11 石 墨 材 料 12 金 屬 矽 13 碳 材 料 14 石 墨 材 料 之 邊 緣 面 15 石 墨 材 料 之 基 礎 面 312XP/發明說明書(補件)/93-12/93129041 395 Separator 6 Insulation pad 7a Current collector 7b Current collector 11 Graphite material 12 Metal 矽 13 Carbon material 14 Edge surface of graphite material 15 Base surface of graphite material 312XP / Invention manual (supplement) / 93-12/93129041 39

Claims (1)

1258883 十、申請專利範圍： 1 . 一種複合粒子，其特徵為，係將可與鋰合金化之金屬 的至少一部分與選自石墨材料及碳材料所組成群組之至少 1材料接觸，且該金屬周圍之孔隙相對於總孔隙為2 0 v〇1 %以上之含有該金屬、該石墨材料及該碳材料。 2 .如申請專利範圍第1項之複合粒子，其中，該石墨材 料係選自鱗片狀石墨及纖維狀石墨所組成群組之至少1材 料。 3 .如申請專利範圍第1項之複合粒子，其中，該石墨材 料為鱗片狀，且拉曼光譜之D帶域的波峰強度對於G帶域 的波峰強度比未滿0 . 4。 4.如申請專利範圍第1項之複合粒子，其中，該石墨材 料係X射線繞射之平均晶格面間隔d G 〇 2在0 . 3 4 n m以下之纖 維狀石墨。 5 .如申請專利範圍第1項之複合粒子，其中，該金屬之 至少一部份接觸於纖維狀石墨材料，且該等之至少外表面 之一部分係以碳材料被覆。 6 .如申請專利範圍第5項之複合粒子，其中，該複合粒 子進一步含有鱗片狀石墨。 7 .如申請專利範圍第1項之複合粒子，其中，該金屬為 石夕。 8 .如申請專利範圍第1項之複合粒子，其中，該金屬之 平均粒徑為0 . 0 1〜1 0 # m。 9 .如申請專利範圍第1項之複合粒子，其中，該金屬為 40 312XP/發明說明書(補件)/93-12/93129041 1258883 非晶質。 I 0 .如申請專利範圍第1項之複合粒子，其中，該複合 粒子之比表面積為20m2/g以下。 II .如申請專利範圍第1項之複合粒子，其中，該複合 粒子之平均粒徑為1〜5 0 // m。 1 2 . —種鋰離子二次電池用負極材料，其特徵為，含有 申請專利範圍第1至1 1項中任一項之複合粒子。 1 3 . —種鋰離子二次電池用負極，其特徵為，使用申請 專利範圍第1 2項之鋰離子二次電池用負極材料。 1 4 . 一種鋰離子二次電池，其特徵為，使用申請專利範 圍第1 3項之鋰離子二次電池用負極。 1 5 . —種複合粒子，係由石墨質材料透過碳質材料而與 可和鋰合金化之金屬一體化者，其特徵為，該複合粒子具 有孔隙，且金屬周圍之孔隙相對於該複合粒子之總孔隙的 比例為2 0 %以上。 41 312XP/發明說明書(補件)/93-12/93129〇411258883 X. Patent application scope: 1. A composite particle characterized in that at least a part of a metal alloyable with lithium is contacted with at least one material selected from the group consisting of a graphite material and a carbon material, and the metal The surrounding pores contain the metal, the graphite material and the carbon material with respect to the total pores of more than 20 v〇1%. 2. The composite particle of claim 1, wherein the graphite material is at least one selected from the group consisting of flaky graphite and fibrous graphite. 3. The composite particle of claim 1, wherein the graphite material is scaly, and the peak intensity of the D-band of the Raman spectrum is less than 0.4 of the peak intensity of the G-band. 4. The composite particle according to claim 1, wherein the graphite material is a fibrous graphite having an average lattice spacing d G 〇 2 of 0.34 n m or less by X-ray diffraction. 5. The composite particle of claim 1, wherein at least a portion of the metal is in contact with the fibrous graphite material, and at least a portion of the outer surface is coated with a carbon material. 6. The composite particle of claim 5, wherein the composite particle further comprises flaky graphite. 7. The composite particle of claim 1, wherein the metal is Shi Xi. 8. The composite particle according to claim 1, wherein the average particle diameter of the metal is 0. 0 1 to 1 0 # m. 9. The composite particle of claim 1, wherein the metal is 40 312XP/invention specification (supplement)/93-12/93129041 1258883 amorphous. The composite particle of the first aspect of the invention, wherein the composite particle has a specific surface area of 20 m 2 /g or less. The composite particle of claim 1, wherein the composite particle has an average particle diameter of from 1 to 5 0 // m. A negative electrode material for a lithium ion secondary battery, which comprises the composite particles according to any one of claims 1 to 11. A negative electrode for a lithium ion secondary battery, which is characterized in that the negative electrode material for a lithium ion secondary battery of claim 12 is used. A lithium ion secondary battery characterized by using the negative electrode for a lithium ion secondary battery of the thirteenth aspect of the patent application. 1 5 . A composite particle which is formed by a graphite material passing through a carbonaceous material and integrated with a metal alloyable with lithium, characterized in that the composite particle has pores, and pores around the metal are relative to the composite particle The ratio of the total pores is more than 20%. 41 312XP/Invention Manual (supplement)/93-12/93129〇41
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