200414579 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種放電容量大且初期充放電效率高、而 且急速放電特性及循環特性亦都優良的鋰離子二次電池 及其構成材料。具體上，係關於一種由至少2種以上不同 物性材料所構成的複合黑鉛粒子及其製造方法，以及使用 該複合黑鉛粒子之負極材料及鋰離子二次電池。 【先前技術】 近年，隨著電子機器的小型化或是高性能化，對電池的 高能量密度化之要求越來越高。鋰離子二次電池與其他二 次電池比較，因為可以高電壓化使能量密度得以提高，所 以受到注目。鋰離子二次電池之主要構成要素是負極、正 極及非水電解質，在放電及充電過程中，從非水電解質所 產生鋰離子在負極及正極間移動而構成二次電池。 通常上述的經離子二次電池之負極材料是使用碳材。作 為這樣的碳材，顯示充放電特性特別優良、大放電容量及 電位平坦性之黑鉛被認為有希望。（日本專利特公昭 6 2 - 2 3 4 3 3號公報等）。 黑鉛，由縮合多環六角網平面（在本發明亦稱為碳網面） 所構成之三因次結晶規則性（在本發明亦稱為結晶性）越 發達，越容易與鋰安定形成層間化合物。因而，由於黑鉛 的結晶性越高，可以有多量的鋰***碳網面的層間，有報 告認為可以增大放電容量（電氣化學及工業物理化學、 6 1(2)，1 3 8 3 ( 1 9 9 3 )等）。依照該碳網面層的***量而形成 312/發明說明書(補件)/93-02/92136136 200414579 種種的層構造，有報告認為此等在共存領域是平坦而且顯 示與經金屬接近的高電位（J.Electrochem. Soc.， V〇l. 1 4 0 , 9 , 2 4 9 0 ( 1 9 9 3 )等）。因而，使用黑鉛作為負極材料來 裝配鋰離子二次電池時，有可能得到高輸出功率。一般而 言，使用黑鉛作為負極材料時之理論電容量，規定為在最 後時黑鉛與鋰形成理想的黑鉛層間化合物L i C 6時之放電 容量，此限界放電容量為372mAh/g。 但是，將黑鉛作為負極材料之鋰離子二次電池，黑鉛的 結晶性越高，初次充電時越容易在黑鉛表面發生電解液分 解等副反應。此副反應會使分解生成物在黑鉛表面堆積成 長，繼續成長至黑鉛的電子無法在溶媒等當中直接移動左 右之厚度。因為初次充電時的副反應與電池反應無關，所 以並無法在放電過程作為電量取出之所謂的不可逆電容 量顯著增加，亦即，有初次放電容量對初次充電容量的比 率（在本發明，亦稱為初期充放電效率）降低問題 (J. Electrochem. Soc·， V ο 1 . 117 222(1970)等）。不可 逆電容量如下式所示。 不可逆電容量=初次的充電容量-初次的放電容量 又，有報告認為因為溶媒分子與鋰離子進行相互*** (c 〇 - i n t e r c a 1 a t e )使黑船表面層剝落、新露出之黑船表面 與電解液反應，導致初期充放電效率降低（J . E 1 e c ΐ r 〇 c h e m S o c. , V o 1 . 1 3 7, 2 0 0 9 ( 1 9 9 0))° 作為補償如此初期充放電效率降低的機構，已知有追加 二次電池正極材料的方法，但是追加過多的正極材料，會 6 312/發明說明書(補件)/93-02/92】36136 200414579 發生能量密度減少之新問題。 如上所述，使用黑鉛作為負極材料之鋰離子二次電池， 欲同時兼備大放電容量與高初期充放電效率，依賴黑鉛結 晶度是兩難的要求。 解決此問題的方法，是以對增大放電容量有利的高結晶 性黑鉛為核心，有二層構造的方法被提案，因為低結晶性 的碳，對放電容量小的電解液，分解反應性較低。 使用如此結晶性不同之二層構造碳材，與以往的技術大 致區別如下。 (1) 在作為核心之高結晶性表面，被覆由丙烷、苯等有 機化合物的熱分解氣體所導入之低結晶性碳。（例如，日 本專利特開平4 - 3 6 8 7 7 8號公報、特開平5 - 2 7 5 0 7 6號公 報）。 (2 ) 在作為核心之高結晶性黑鉛上，被覆或含浸液相之 瀝青（p i t c h )、固化性樹脂等後，以1 0 0 0 °C煅燒，在表面 層形成低結晶性碳（例如，日本專利特開平4 - 3 6 8 7 7 8、特 開平5 - 9 4 8 3 8號公報、特開平5 - 2 1 7 6 0 4號公報、特開平 6 - 8 4 5 1 6號公報、特開平0 7 - 3 0 2 5 9 5、特開平1 1 - 5 4 1 2 3號 公報、特開2 0 0 0 - 2 2 9 9 2 4號公報、特開2 0 0 0 - 3 7 0 8號公報）。 但是，關於近年來對放電容量的增大的要求水準，任何 一者方法仍都不能說是充分。 上述（1 )的方法，從工業生產的觀點，有製造步驟麻煩 且成本高之生產率上的問題。又，由於表面被覆有極薄膜 狀之低結晶性碳，有比表面積高、初期充放電效率低的問 312/發明說明書(補件)/93-02/92136136 200414579 題存在。 又，上述（2 )的方法，在1 0 0 0 °C左右煅燒時表面的低結 晶性碳之間會產生熔融黏著，將其粉碎時表層的低結晶碳 會從核心之黑热表面層剝落，有比表面積和鬆密度（b u 1 k d e n s i t y )等粉體特性、初期充放電效率等電池特性降低的 問題存在。 又，在上述（1 )及（2 )的方法，核心之黑鉛與表層之低結 晶性碳，因伴隨充放電所產生的不同膨漲、收縮動作，隨 著反覆進行急速充放電時和充放電，表層的低結晶性碳發 生剝落，也會引起上述同樣的問題。 電池的放電容量大大地依賴於構成負極之黑鉛之單位 容積放電容量。因而，為了增大電池的放電容量，高密度 充填每單位重量放電容量（m A h / g )大的黑鉛是有利的。但 是高密度充填黑鉛來形成負極時，在上述（1 )及（2 )的方 法，黑鉛與表層低結晶性碳之黏著力常常不足，於是，低 結晶性碳的被覆膜會從黑鉛剝落，露出與電解液反應性高 的黑鉛表面致使初期充放電電效率降低。 又，在日本專利特開2 0 0 0 - 3 7 0 8號公報，以瀝青被覆黑 鉛後，以2 8 0 0 °C熱處理亦在實施例顯示，但是所形成的被 覆膜結晶性低（拉曼分光的R值為 0 . 3 2，R值的測定法後 述），發生上述同樣的問題。又，雖然使用斜邊鱗片狀黑 鉛為芯材，但是黑鉛寬高比大，製成負極時黑鉛的定向作 用亦招致急速放電特性和循環特性的降低。 上述以往技術之外，在複合黑鉛的粒子形狀接近球狀之 3丨2/發明說明書(補件)/93-02/92〗36136 200414579 曰本專利特開2 0 0 1 - 8 9 1 1 8號公報的情況，急速充放電特 性和循環特性被認定有一定的效果。但是，該公報未提到 最外層與内部的結晶性之差異。從該製法是將複數偏平狀 的焦炭與瀝青混合、煅燒，粉碎成寬高比在為5以下後黑 鉛化來看，只能得到高結晶性的複合黑鉛粒子而已，初期 充放電效率仍然低落。 【發明内容】 本發明的目的，在於得到一種使用黑鉛作為鋰離子二次 電池的負極材料時，兼備以往視為兩難之性能、亦即大放 電容量和高初期充放電效率等兩項性能，同時急速放電特 性和循環特性亦優良之鋰離子二次電池。具體上，本發明 的目的在於提供一種能夠滿足該性能之新複合黑鉛粒子 及其製造方法，以及使用該複合黑鉛之負極材料及鋰離子 二次電池。 亦即本發明提供一種複合黑鉛粒子，在X線繞射的面間 隔d 0。2未滿0 . 3 3 7 n m之黑鉛的至少在表面部分具有比該 黑鉛更低結晶性的碳材之複合黑鉛粒子，該複合黑鉛粒子 的寬高比在3以下，該複合黑鉛粒子0 . 5〜2 0質量％為該碳 材，該複合黑錯粒子在拉曼光譜（R a m a n s p e c t r u m )，對 1 5 8 0 c m_ 1之尖鋒強度（I ! 5 8 〇)，1 3 6 0 c m _1之尖鋒強度（I ! 3") 的比（I 1 5 8 (J / I 1 3 t5 0 )為0 . 1以上至未滿0 . 3。又，此複合黑 鉛粒子，以在該碳材之X線繞射的面間隔d 。〇2未滿 0 . 3 4 3 n m，而且對該黑鉛的面間隔d 〇 g 2比在1 . 0 0 1以上至 未滿1 . 0 2為佳。 9 312/發明說明書(補件)/93-02/92136 200414579 此外，任何一種複合黑鉛粒子，該黑鉛都是以造粒成為 鱗片狀為佳。 又，本發明亦提供一種複合黑鉛粒子，係在使用機械外 力將鱗片狀黑鉛造粒成為球狀黑鉛粒子上，被覆碳化物層 (將樹脂單獨或是樹脂與瀝青之混合物加熱碳化而成、換 算為碳量在0 . 5〜2 0質量％ )而成。 此外，本發明亦提供一種係對使用機械外力將鱗片狀黑 鉛賦形造粒成為球狀黑鉛粒子，混合可碳化材料（含有從 熱固性樹脂、熱固性樹脂前身以及熱固性樹脂原料之混合 物所構成群體中選出至少一種樹脂材料）、碳化，使被覆 0 . 5〜2 0質量％之碳化材料而成之複合黑鉛粒子。又，此複 合黑鉛粒子以使用該可碳化材料是該樹脂材料與焦油類 之混合物，且該樹脂材料/焦油類之質量比=5 / 9 5〜1 0 0 / 0為 佳。 又，上述之任何一種複合黑鉛粒子，該樹脂材料都是以 從酚醛樹脂、酚醛樹脂前身及酚醛樹脂之單體所構成群體 選出至少一種為佳。 此外，本發明亦提供含有在上述所開示之任何一種複合 黑鉛粒子之鋰離子二次電池負極材料。又，本發明亦提供 使用此等任何一種負極材料之鋰離子二次電池。 此外，本發明亦提供一種複合黑鉛粒子之製造方法，含 有使用機械外力將鱗片狀黑鉛造粒成為球狀黑鉛粒子之 造粒步驟、為使後面的碳化步驟所得到的複合黑鉛粒子之 8 0〜9 9 . 5 %係該造粒化黑鉛而在所得到的造粒化黑鉛上混 10 312/發明說明書(補件)/93-02/92136136 200414579 合含有從熱固性樹脂、熱固性樹脂前身以及熱固性樹脂原 料之混合物所構成群體中選出至少一種樹脂材料之可碳 化材料之步驟、以及將所得到的混合物以2 0 0 0 °C〜3 2 0 0 °C 進行碳化之步驟。又，在此製造方法，該可碳化材料是該 樹脂材料與焦油類之混合物，且該樹脂材料/焦油類之質 量比=5 / 9 5〜1 0 0 / 0 (質量比）為佳。 又，在任何一種製造方法，該樹脂材料都是以從酚醛樹 脂、酚醛樹脂前身及酚醛樹脂之單體所構成群體選出至少 一種為佳。 此外，在上述任何一種製造方法，都是在該碳化步驟之 前，進一步地對該樹脂材料以2 0 0 °C〜3 0 0 °C進行熱固化步 驟更佳。 【實施方式】 以下詳細說明本發明。 本發明係在X線繞射的面間隔d 〇。2未滿0 . 3 3 7 π m之黑 鉛的至少在表面部分具有比該黑鉛更低結晶性的碳材之 複合黑鉛粒子，該複合黑鉛粒子的寬高比在3以下，該複 合黑鉛粒子0 . 5〜2 0質量％為該碳材，該複合黑鉛粒子在拉 曼光譜（Raman spectrum)，對於 1580(：111_1 之尖鋒強度（Ιΐ58〇) 相對於1 3 6 0 C丨1】_ 1之尖鋒強度（I 1 3 G ◦)的比（I 1 5 8 G / I 1 3 6 0 )為0 . 1 以上至未滿0 . 3之複合黑鉛粒子。 (黑鉛） 構成本發明複合黑鉛粒子芯材之黑鉛，係顯示X線繞射 的面間隔d 〇 〇 2未滿0 . 3 3 7 π πι之南結晶性黑热5這樣的黑 11 3丨2/發明說明書(補件)/93-02/92136136 200414579 雜，例如市售鱗片狀天然黑鉛具有代表性。結晶性越高的 黑鉛，結晶性有規則地成長，一般呈現鱗片狀。又，因為 最終所得到的複合黑鉛粒子之形狀是反映此黑鉛的形 狀，所以黑鉛的形狀以接近球狀為佳，使用寬高比（粒子 的長軸長度對短軸長度之比）在3以下之黑鉛為佳。這樣 的黑船，例如，可以用鱗片狀 方法製造。可以利用市售品、 黑鉛等各種形狀的黑鉛來作為 鉛、人造黑鉛等非鱗片狀黑鉛 道的粉碎裝置加以粉碎成鱗片 以使用粒子計數器氣流式研磨 (Hosokawamicron(股）製）、氣 (曰清Engineering(股）製）等 鱗片狀黑鉛，其表面具有銳角 力於此鱗片狀黑鉛、賦形使成 造粒化黑鉛為佳。此造粒步驟 鱗片狀黑鉛，調製成寬高比在 在本發明並未排除單獨使用粉 加外加來賦形成為球狀的方法 如，可以舉出的有，在黏合劑、 混合複數鱗片狀黑鉛的方法、 狀黑鉛施加機械外力的方法、 用造粒助劑下對複數鱗片狀黑 佳。作為造粒裝置，可以使用 黑鉛作為原料，採用以下的 或是粗粒的天然黑錯和人造 鱗片狀黑鉛。在粗粒天然黑 的情況，首先是使用眾所知 狀為佳。作為粉碎裝置，可 機（Counter jet mill) 流式研磨機（C u r r e n t jet) 。雖然經由粉碎等所得到的 部分，在本發明施加機械外 為球狀，使成為表面平滑之 通常使用複數粉碎所得到的 3以下之造粒化黑鉛。但是， 碎所得到的鱗片狀黑鉛。施 ，並沒有特別的限制，例 樹脂等造粒助劑的共存下， 不使用黏合劑下對複數鱗片 及兩者並用等。但是以不使 鉛施加機械外力的一方更 GRANUREX (Freund 產業（股） 312/發明說明書(補件)/93-02/92丨36136 12 200414579 製）、NEW GRAMACHINE (Seishin(股）製）、AGUROMASTER (Hosokawainicron (股）製）等造粒機、HIBRIDIGESTION S Y S T E Μ (奈良機械製作所（股）製）、Μ E G A N 0 Μ I C R〇X (奈良 機械製作所（股）製）、MEK AN OF US I ON SYSTEM (Hosokawaniicron (股）製）等具有剪切壓縮加工能力的裝 置，又，使用上述的粉碎裝置藉由操作運轉條件亦可以造 粒。 賦形成為球狀的造粒化黑鉛，可以由一個鱗片狀黑鉛揉 圓而成，亦可以由數個鱗片狀黑鉛集合造粒而成，特別是 以複數鱗片狀黑鉛造粒成呈現同心圓形狀為佳。 作為構成本發明的複合黑鉛粒子之芯材黑鉛，如果具體 上舉出之更合適的規格，平均粒徑為5〜6 0 // m、寬高比在 3以下、比表面積為0 . 5〜1 0 m2 / g、在X線繞射微晶 (crystallite)之C軸方向的大小（Lc)為40nm以上、d 〇〇2 為未滿0.337nm及使用氬雷射（Argon laser)經由拉曼分 光法所測定得到的1 3 6 0 c πΓ 1譜帶強度（I , 3 6 〇)與1 5 8 0 c πΓ 1譜 帶強度（Il58G)之比（Il36〇/Il58G)(R 值）為 0.06 〜0.25、以及 1 5 8 0 c πΓ 1譜帶強度的半值幅度為1 〇〜6 0。 (碳材） 本發明之複合黑鉛粒子，係黑鉛的至少在表面部分為碳 材所被覆。碳材若能夠賦與後述複合黑鉛粒子性狀，任何 的碳材都可以。通常，該碳材以在上述造粒化黑鉛上，塗 布、含浸及/或混合可碳化材料後，經加熱碳化處理所得 到的為佳。本發明所稱可碳化材料，是指經加熱碳化及/ 312/發明說明書(補件)/93-02/92] 36136 13 200414579 或黑热化所得到的材料。如此的加熱，一般是在7 0 0 °C以 上，以8 Ο 0〜3 2 Ο 0 °C為佳。因而，本發明所稱碳化處理，亦 包含黑鉛化處理，以2 0 0 0〜3 2 0 0 °C為特佳。又，本發明所 稱黑鉛的至少在表面部分，是指黑鉛外表面的全部或是其 一部分，本發明亦有典型例，在造粒化黑鉛是由複數的（鱗 片狀）黑鉛所構成之二次粒子的情況，是指此二次粒子的 外表面或是其一部分，在這樣二次粒子的情況，有時可碳 化材料會侵入二次粒子的内部而碳化。當然有時亦會在黑 鉛單體的内部形成該碳材。但是本發明的複合黑鉛粒子， 以該黑鉛的全外表面為該炭素材料所被覆為最合適，合適 的被覆率為5 0〜1 0 0 %。 又，本發明之上述可碳化材料，以樹脂材料和焦油類的 混合物、該樹脂材料對該焦油類的質量比為該樹脂材料/ 該焦油類=5 / 9 5〜1 0 0 / 0為佳，更佳的是3 0 / 7 0〜7 0 / 3 0。該 樹脂材料的比率若在5 %以上時，所形成的碳化物層的黑錯 化（結晶化）充分地進行之同時，初期充放電效率的提高效 果亦變大。混合使用該樹脂材料與該焦油類，可以調整碳 材的黑鉛化度（結晶性），使本發明的效果達到最大，是符 合希望的。 本發明所稱焦油類，是指木材乾餾時所生成的焦油、從 煤所得到的煤焦油（c 〇 a 1 t a r )、從石油所生產的重質油等 碳材前身，包含將此等作為原料加以縮聚 (polycondensation)而成之物。具體上，煤系遞青、主體 中間相遞青（b u 1 k m e s 〇 p h a s e p i t c h )、石油系瀝青等亦包 14 3 12/發明說明書(補件)/93-02/92136136 200414579 含在本發明的焦油類中。此等分別單獨以3 0 0 0 °C左右熱處 理時會生成黑鉛構造，在光學上是各向同性（i s o t r o p y )或 是各向異性（anisotropy)均可。 本發明所稱樹脂材料，是指從樹脂本身、樹脂的前身及 樹脂的合成原料之混合物所構成的群體中選出至少一 種，此樹脂的前身亦包含反應中間體和低聚合物 (◦ 1 i g 〇 m e 1-)或是聚合中間體等。若例示樹脂的合成原料之 混合物，例如將含有單體類、聚合引發劑等之混合物，經 由攪拌及放置等所得到樹脂之混合物。 在本發明作為該樹脂材料，以從熱固化性樹脂、熱固化 性樹脂的原料之混合物及熱固化性樹脂的前身所構成的 群體中選出至少一種為佳。 以高溫來碳化熱固化性樹脂類所得到的碳化物，雖然亦 含有平均具有黑鉛相當的高結晶性之黑鉛部分，但是因為 亦含有具有碳亂層構造部分，本發明稱為碳材來與芯材黑 鉛作區別稱呼。 作為熱固化性樹脂，以經由熱處理、殘存碳量多的為 佳，可以舉出的有尿素樹脂、順丁烯二酸樹脂（m a 1 e i c acid)、香豆0同樹脂（c o u m a r ο n e r e s i n )、二甲苯樹脂和酉分 酸樹脂等。 在本發明作為該樹脂材料，以使用從酚醛樹脂、酚醛樹 脂的原料之混合物及酚醛樹脂的前身所構成的群體中選 出至少一種更佳。若更具體地例示，可以使用酚醛樹脂本 身（具有取代基亦可之以苯酚類與曱醛為代表的醛類之高 15 3丨2/發明說明書(補件)/93-02/92136丨36 200414579 度縮合物）、苯酚類與醛類之初期縮合物（酚醛樹脂的前 身）、及苯酚類與醛類之混合物（單體混合物）等之任何一 者。 構成本發明複合黑鉛粒子碳材的結晶性，比芯材黑鉛更 低’以X線繞射的面間隔d 〇。2未滿0. 3 4 3為佳’ X線繞射 的面間隔d 。。2若未滿0.343’可以使放電容量更為提南’ 也提高碳材與黑鉛的黏著性。黑鉛與碳材的結晶性之差， 以碳材的d。。2對黑船的d。。2比在1 . 0 0 1以上至未滿1 . 0 2 的範圍為佳。在1 . 0 0 1以上時，可以使初期充放電效率更 為提高，在未滿1 . 0 2的一方，也能夠提高碳材的黏著性。 (複合黑鉛粒子） 再一次地顯示本發明的複合黑鉛粒子係在X線繞射的面 間隔d 。。2未滿0 . 3 3 7 n m之黑鉛的至少在表面部分具有比 該黑鉛更低結晶性的碳材之複合黑鉛粒子，該複合黑鉛粒 子的寬高比在3以下，該複合黑鉛粒子0 . 5〜2 0質量％為該 碳材，該複合黑船粒子在拉曼光譜（R a m a n s p e c t r u m )，對 於1580cm_1之尖鋒強度（I158〇)相對於1360cm_1之尖鋒強度 (I 1 3 6 Q )的比（I 1 5 8。/ I 1 3 6。）為0 . 1以上至未滿0 · 3複合黑錯 粒子，並且更詳細地說明。 該複合黑鉛粒子亦有寬高比在3以下、形狀接近球狀之 特徵。以上述的黑鉛作為芯材，至少在表面部分具有比該 黑鉛更低結晶性的碳材存在。可以用拉曼分光法的R值來 規定該複合黑鉛粒子的表面結晶性，使用氬雷射（A r g ο η 1 a s e r )經由拉曼分光法所測定得到的1 3 6 0 c πΓ 1譜帶強度 16 312/發明說明書(補件)/93-02/92136136 200414579 (Il3 60)與 1580cm 1 譜帶強度（Il58G)之比（Ii3Gg/Ii580)(R 值） 必須在0 . 1以上未滿0 . 3。R值未滿0 . 1或是0 . 3以上時， 會使初期充放電效率降低，R值以0 . 1〜0 . 2為特佳。 又，本發明之該碳材的比率，以碳量換算來表示，規定 碳材佔有複合黑鉛粒子的比率在0 . 5〜2 0質量％的範圍，此 比率對應該造粒化黑鉛佔有複合黑鉛粒子的比率在 8 0〜9 9 . 5 %。碳化步驟後，在混合該可碳化材料來使造粒化 黑鉛佔有複合黑鉛粒子的比率在8 0〜9 9 . 5 %時，因為所選擇 之可碳化材料的種類而有不同的殘碳率，無法一概地規 定。但是，通常對造粒化黑鉛，混合可碳化材料大約1〜7 0 質量％左右。若顯示更具體的例子，可碳化材料為酚醛樹 脂的情況等，混合2〜5 0質量％左右，以2 0〜3 5質量％左右 為佳，若參考其來進行適當的試驗時，可以找出適當的混 合比率。碳材佔有複合黑鉛粒子的比率未滿0 . 5質量％時， 欲完全被覆活性黑鉛的邊緣面變為困難，初期充放電效率 會降低，另一方面，超過2 0質量％時，相對地，放電容量 低的碳材的比率增力口，複合黑鉛粒子的放電容量會降低。 又，用以形成碳材的原料（熱固化性樹脂類和焦油遞青類） 的比率大時，在被覆步驟和其後的熱處理步驟，粒子容易 熔融黏著，最後所得到的複合黑鉛粒子的碳材層之一部分 會發生破裂、剝離，致使初期充放電效率降低，該碳材的 比率，特別是以3〜1 5質量％、進而以8〜1 2質量％為佳。 此外，若舉出本發明的複合黑鉛粒子之理想物性值，平 均粒子徑為5〜6 0 " m、比表面積為0 , 5〜1 0 m2 / g、在X線繞 17 3 12/發明說明書(補件)/93-02/92136丨36 200414579 射微晶（c r y s t a 1 1 i t e )之C軸方向的大小（ 上、d。。2為未滿0 . 3 3 7 η hi為佳。平均粒徑 定值範圍内，放電容量和初期充放電效率 放電特性和循環特性等其他的電池特性亦 表面積若未滿1 0 m2 / g，形成負極時的負極 料與膠黏劑分散液的混合物）之黏度調整笔 膠黏劑而來的黏著力提高。X線繞射的Lc 定值内時，可以得到充分的放電容量。 又，在本發明，因為該碳材以被覆在該 佳，所以也可以用碳化層來表達該複合黑 的部分。 (複合黑鉛粒子的製造方法） 本發明亦提供一種複合黑鉛粒子之製造 機械外力將鱗片狀黑鉛造粒成為球狀黑鉛 驟、為使後面的碳化步驟所得到的複合黑 8 0〜9 9 . 5 %係該造粒化黑船而在所得到的造 合含有從熱固性樹脂、熱固性樹脂前身以 料之混合物所構成群體中選出至少一種樹 化材料之步驟、以及將所得到的混合物以 進行碳化之步驟。 例示本發明的複合黑鉛粒子之製造方法 以使用如上所述經由造粒操作等預先賦形 在此造粒化黑鉛上被覆熱固化性樹脂類單 樹脂類與焦油類之混合物時，例如，在混 3 12/發明說明書(補件)/93-02/92136136200414579 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a lithium ion secondary battery having a large discharge capacity, high initial charge-discharge efficiency, and excellent rapid discharge characteristics and cycle characteristics, and a constituent material thereof. Specifically, the present invention relates to a composite black lead particle composed of at least two different physical properties and a method for producing the same, and a negative electrode material and a lithium ion secondary battery using the composite black lead particle. [Previous technology] In recent years, with the miniaturization or high performance of electronic devices, the demand for higher energy density of batteries has become higher and higher. Compared with other secondary batteries, lithium-ion secondary batteries have attracted attention because they can increase the voltage and increase the energy density. The main components of a lithium ion secondary battery are a negative electrode, a positive electrode, and a non-aqueous electrolyte. During discharge and charging, lithium ions generated from the non-aqueous electrolyte move between the negative electrode and the positive electrode to form a secondary battery. Generally, a carbon material is used as the negative electrode material of the above-mentioned ion secondary battery. As such a carbon material, black lead showing particularly excellent charge-discharge characteristics, large discharge capacity, and potential flatness is considered promising. (Japanese Patent Publication No. 6 2-2 3 4 3 3, etc.). Black lead, a three-dimensional crystal regularity (also referred to as crystallinity in the present invention) composed of a condensed polycyclic hexagonal mesh plane (also referred to as a carbon mesh surface in the present invention), the more developed, the easier it is to form an interlayer with lithium stability. Compounds. Therefore, due to the higher crystallinity of black lead, a large amount of lithium can be inserted between the layers of the carbon mesh surface, and there are reports that the discharge capacity can be increased (Electrical Chemistry and Industrial Physical Chemistry, 6 1 (2), 1 3 8 3 ( 1 9 9 3), etc.). Various layer structures of 312 / Invention Specification (Supplement) / 93-02 / 92136136 200414579 are formed according to the amount of the carbon mesh surface layer inserted, and it is reported that these are flat in the coexistence field and show a high potential close to that of the metal (J. Electrochem. Soc., Vol. 1 40, 9, 2 4 9 0 (19 9 3), etc.). Therefore, it is possible to obtain high output power when assembling a lithium ion secondary battery using black lead as a negative electrode material. In general, the theoretical capacitance when black lead is used as a negative electrode material is specified as the discharge capacity when black lead and lithium form the ideal black lead interlayer compound L i C 6 at the end, and this limit discharge capacity is 372 mAh / g. However, in a lithium ion secondary battery using black lead as a negative electrode material, the higher the crystallinity of black lead, the more easily side reactions such as electrolyte decomposition occur on the surface of black lead during the first charge. This side reaction causes the decomposition products to accumulate and grow on the surface of black lead, and the electrons that continue to grow until the black lead cannot move directly in the solvent or the like by a thickness. Because the side reaction at the time of initial charging has nothing to do with the battery reaction, the so-called irreversible capacity that cannot be taken out as electricity during the discharge process significantly increases, that is, there is the ratio of the first discharge capacity to the first charge capacity (in the present invention, also known as (Initial charge and discharge efficiency) to reduce the problem (J. Electrochem. Soc ·, V ο 1. 117 222 (1970), etc.). The irreversible capacitance is shown in the following formula. Irreversible capacitance = initial charge capacity-initial discharge capacity. It has been reported that the surface of the black ship is peeled off due to the intercalation of solvent molecules and lithium ions (c 0-interca 1 ate). Liquid reaction, resulting in lower initial charge-discharge efficiency (J. E 1 ec ΐ r 〇chem S o c., V o 1. 1. 3 7, 2 0 0 9 (1 9 0)) ° as compensation for such initial charge and discharge As a mechanism for reducing efficiency, a method for adding a positive electrode material for a secondary battery is known, but if too much positive electrode material is added, 6 312 / Invention Specification (Supplement) / 93-02 / 92] 36136 200414579 will cause a new problem of reduced energy density. . As described above, a lithium ion secondary battery using black lead as a negative electrode material is required to have both a large discharge capacity and a high initial charge-discharge efficiency, and depends on the black lead crystallinity. The solution to this problem is to use a highly crystalline black lead, which is advantageous for increasing the discharge capacity, as a core, and a two-layer structure has been proposed. Because of low crystalline carbon, it has decomposition reactivity to electrolytes with a small discharge capacity. Lower. The use of such a two-layer structure carbon material having a different crystallinity is substantially different from the conventional technology as follows. (1) The highly crystalline surface as the core is covered with low-crystalline carbon introduced by the thermal decomposition gas of organic compounds such as propane and benzene. (For example, Japanese Patent Laid-Open No. 4-3 6 8 7 7 8 and Japanese Patent Laid-open No. 5-2 7 5 0 7 6). (2) After coating or impregnating liquid phase pitch and curable resin on the highly crystalline black lead as the core, it is calcined at 1000 ° C to form low crystalline carbon on the surface layer (for example, , Japanese Patent Laid-open No. 4-3 6 8 7 7 8, Japanese Patent Laid-open No. 5-9 4 8 3, Japanese Laid-open Patent No. 5-2 1 7 6 0 4 and Japanese Laid-Open Patent No. 6-8 4 5 1 6 Japanese Unexamined Patent Publication No. 0 7-3 0 2 5 9 5. Japanese Unexamined Patent Publication No. 1 1-5 4 1 2 Japanese Unexamined Patent Publication No. 2 0 0 0-2 2 9 9 2 Japanese Unexamined Patent Publication No. 2 0 0 0-3 7 0 8). However, with regard to the level of demand for an increase in the discharge capacity in recent years, neither method can be said to be sufficient. The method (1) described above has a problem in that the production steps are troublesome and the productivity is high from the viewpoint of industrial production. In addition, since the surface is coated with extremely thin film-like low-crystalline carbon, there is a problem that the specific surface area is high and the initial charge / discharge efficiency is low 312 / Invention Specification (Supplement) / 93-02 / 92136136 200414579. In the method (2) above, the low-crystalline carbons on the surface are calcined at a temperature of about 1000 ° C, and the low-crystalline carbons on the surface layer are peeled off from the core black hot surface layer when they are crushed. There are problems that powder characteristics such as specific surface area and bulk density (bu 1 kdensity) and battery characteristics such as initial charge and discharge efficiency are reduced. In the methods (1) and (2) above, the core black lead and the low-crystalline carbon on the surface layer have different expansion and contraction actions due to charge and discharge, and they are repeatedly charged and discharged during rapid charge and discharge. Discharge and peeling of the low-crystalline carbon in the surface layer cause the same problems as described above. The discharge capacity of a battery greatly depends on the discharge capacity per unit volume of the black lead constituting the negative electrode. Therefore, in order to increase the discharge capacity of the battery, it is advantageous to fill black lead with a high discharge capacity (m Ah / g) per unit weight. However, when black lead is filled at a high density to form a negative electrode, in the methods (1) and (2) described above, the adhesion between black lead and low-crystalline carbon on the surface layer is often insufficient, so the coating film of low-crystalline carbon will change from black. Lead is peeled off and exposed to the surface of black lead, which is highly reactive with the electrolytic solution, resulting in a decrease in initial charge and discharge efficiency. Also, in Japanese Patent Laid-Open No. 2000-7000, after black lead is coated with asphalt, heat treatment at 2800 ° C is also shown in the examples, but the formed film has low crystallinity. (The R value of Raman spectroscopy is 0.32, and the method of measuring the R value will be described later.) The same problem as described above occurs. In addition, although oblique-scale scaly black lead is used as the core material, the aspect ratio of black lead is large, and the directional effect of black lead when it is used as a negative electrode also causes a decrease in rapid discharge characteristics and cycle characteristics. In addition to the above-mentioned prior art, the particle shape of the composite black lead is close to a spherical shape 3 丨 2 / Invention Specification (Supplement) / 93-02 / 92〗 36136 200414579 Japanese Patent Laid-Open No. 2 0 0 1-8 9 1 1 In the case of Publication No. 8, rapid charge-discharge characteristics and cycle characteristics have been found to have certain effects. However, the publication does not mention the difference in crystallinity between the outermost layer and the inside. From this manufacturing method, a plurality of flat coke is mixed with asphalt, calcined, and pulverized into black lead after the aspect ratio is 5 or less. Only black crystalline composite black lead particles can be obtained, and the initial charge and discharge efficiency is still low. [Summary of the Invention] The purpose of the present invention is to obtain a performance that has been regarded as a dilemma when using black lead as a negative electrode material of a lithium ion secondary battery, that is, a large discharge capacity and a high initial charge and discharge efficiency. A lithium ion secondary battery that is also excellent in rapid discharge characteristics and cycle characteristics. Specifically, an object of the present invention is to provide a new composite black lead particle capable of satisfying this performance, a method for manufacturing the same, and a negative electrode material and a lithium ion secondary battery using the composite black lead. That is, the present invention provides a composite black lead particle having black crystals having a lower crystallinity than the black lead at least on the surface portion of the black lead having an interval d 0. 2 and less than 0.3 3 7 nm in the plane of X-ray diffraction. Composite black lead particles, the composite black lead particles having an aspect ratio of 3 or less, the composite black lead particles 0.5 to 20% by mass of the carbon material, the composite black lead particles in a Ramanspectrum ), The ratio of the peak strength (I! 5 8 〇) of 1 5 0 0 c m_ 1 to the peak strength (I! 3 ") of 1 3 60 cm _1 (I 1 5 8 (J / I 1 3 t5 0) is from 0.1 to less than 0.3. In addition, the composite black lead particles are separated by a distance d from the plane diffracted by the X-ray of the carbon material. 〇2 is less than 0.3 3 nm, In addition, the interplanar interval d 0g 2 of the black lead is preferably greater than 1.0 01 and less than 1.0 2. 9 312 / Description of the Invention (Supplement) / 93-02 / 92136 200414579 The composite black lead particles are preferably granulated into a scaly shape. In addition, the present invention also provides a composite black lead particle which is formed by granulating the scaly black lead into spherical black lead particles using a mechanical external force. , Carbide layer (made by heating and carbonizing the resin alone or a mixture of resin and asphalt, converted to a carbon content of 0.5 to 20% by mass). In addition, the present invention also provides a system The scaly black lead is shaped into spherical black lead particles, mixed with a carbonizable material (containing at least one resin material selected from the group consisting of a mixture of a thermosetting resin, a precursor of the thermosetting resin, and a raw material of the thermosetting resin), carbonized, and the coating is 0 5 ~ 20 mass% of composite black lead particles made of carbonized material. In addition, the composite black lead particles are a mixture of the resin material and tar, and the mass of the resin material / tar is used as the carbonizable material. The ratio is preferably 5/9 5 to 1 0 0 / 0. In addition, for any of the composite black lead particles described above, the resin material is selected from a group consisting of phenolic resin, a precursor of phenolic resin, and monomers of phenolic resin. In addition, the present invention also provides a lithium ion secondary battery negative electrode material containing any of the composite black lead particles disclosed above. Furthermore, the present invention also provides Lithium ion secondary batteries using any of these negative electrode materials. In addition, the present invention also provides a method for manufacturing composite black lead particles, which includes a granulation step of granulating black lead particles into spherical black lead particles using a mechanical external force. In order to make 80 to 99.5% of the composite black lead particles obtained in the subsequent carbonization step, the granulated black lead is mixed with the obtained granulated black lead 10 312 / Invention Specification (Supplement) ) / 93-02 / 92136136 200414579 A step of selecting a carbonizable material containing at least one resin material from the group consisting of a thermosetting resin, a precursor of the thermosetting resin, and a mixture of the raw materials of the thermosetting resin, and a step of dividing the obtained mixture into 2 0 0 0 ° C ~ 3 2 0 0 ° C Carbonization step. In this manufacturing method, the carbonizable material is a mixture of the resin material and tars, and the mass ratio of the resin material / tars is preferably 5/9 5 to 100/100 (mass ratio). In any manufacturing method, the resin material is preferably selected from the group consisting of a phenol resin, a phenol resin precursor, and a monomer of the phenol resin. In addition, in any of the above-mentioned manufacturing methods, it is more preferable that the resin material is further subjected to a thermal curing step at 200 ° C to 300 ° C before the carbonization step. [Embodiment] The present invention will be described in detail below. In the present invention, the interval d 0 is formed on the plane of X-ray diffraction. Composite black lead particles of carbon material having a lead content of less than 0.3 3 3 7 π m at least on the surface portion of a carbon material having a lower crystallinity than the black lead, and the aspect ratio of the composite black lead particles is 3 or less. 0.5 ~ 20% by mass of the composite black lead particle is the carbon material, and the composite black lead particle has a Raman spectrum of 1580 (: 111_1 with a sharp intensity (Ιΐ58〇) relative to 1 3 6 0 C 丨 1】 combined black lead particles whose ratio (I 1 3 G ◦) of _ 1 is (I 1 5 8 G / I 1 3 6 0) is from 0.1 to less than 0.3. Black lead) The black lead constituting the composite black lead particle core material according to the present invention is a black 11 3 such as the crystalline black heat 5 which is south of π π 2 and shows an interplanar interval of X-ray diffraction.丨 2 / Instruction of the Invention (Supplement) / 93-02 / 92136136 200414579 Miscellaneous, such as commercially available scale-shaped natural black lead is typical. The higher the crystallinity of black lead, the crystallinity grows regularly, and it generally appears scaly. In addition, because the shape of the finally obtained composite black lead particles reflects the shape of the black lead, the shape of the black lead is preferably close to a spherical shape, and an aspect ratio (particle size The ratio of the length of the shaft to the length of the short axis is preferably black lead of less than 3. Such a black ship can be manufactured, for example, by a scaly method. Commercially available black lead of various shapes can be used as lead, A non-scaly black lead pulverizing device such as artificial black lead is pulverized into flakes to use a particle counter air-flow grinding (manufactured by Hosokawamicron), flaky black lead such as gas (manufactured by Qing Engineering), and the surface thereof It has an acute angular force on the scaly black lead, and it is preferable to shape it into granulated black lead. In this granulation step, the scaly black lead is adjusted to an aspect ratio. In the present invention, it is not excluded to use powder alone and additionally to add Examples of the method for forming the spheres include a binder, a method of mixing a plurality of scaly black lead, a method of applying a mechanical force to the shape of the black lead, and a scaly black with a granulation aid. The granulation device can use black lead as raw material, and use the following or coarse-grained natural black flakes and artificial scale-like black lead. In the case of coarse-grained natural black, it is better to use a known shape first. As a crushing device Counter jet mill (Current jet). Although the part obtained through pulverization, etc., is spherical outside the machine according to the present invention to make the surface smooth. Usually, it is 3 or less obtained by using multiple pulverization. Granulated black lead. However, the scaly black lead obtained by crushing is not particularly limited. For example, in the coexistence of a granulation aid such as a resin, a plurality of scales and a combination of both are used without using an adhesive. .However, GRANUREX (Freund Industry (stock) 312 / Invention Specification (Supplement) / 93-02 / 92 丨 36136 12 200414579), NEW GRAMACHINE (Seishin (stock) system), AGUROMASTER (Hosokawainicron (manufactured)) and other granulators, HIBRIDIGESTION SYSTE M (Nara Machine Works (manufactured)), M EGAN 0 Μ ICR〇X (Nara Machine Works (manufactured)), MEK AN OF US I ON SYSTEM (Hosokawaniicron (manufactured)) and other equipment with shear compression processing capabilities, and using the above-mentioned pulverizing equipment can be granulated by operating conditions. The granulated black lead that is formed into a spherical shape can be formed by kneading a scaly black lead, or it can be formed by assembling a plurality of scaly black lead, especially by a plurality of scaly black lead. Concentric shapes are preferred. As the core material black lead constituting the composite black lead particles of the present invention, if more specific specifications are specifically listed, the average particle diameter is 5 to 6 0 // m, the aspect ratio is 3 or less, and the specific surface area is 0. 5 to 10 m2 / g, the size (Lc) in the C-axis direction of X-ray diffraction crystallites (crystals) is 40 nm or more, d 〇2 is less than 0.337 nm, and an Argon laser is used to pass Ratio of the band intensity (I, 36) of 136 0 c πΓ 1 (I, 36 〇) and the band intensity (Il58G) of 158 0 c πΓ 1 (R value) measured by Raman spectrometry ) Are 0.06 to 0.25, and the half-value amplitude of the band intensity of 1 580 0 c πΓ is 10 to 60. (Carbon material) The composite black lead particles of the present invention are black lead coated with a carbon material at least on the surface portion. As long as the carbon material can impart the properties of the composite black lead particles described later, any carbon material may be used. Generally, the carbon material is preferably obtained by coating, impregnating, and / or mixing a carbonizable material on the granulated black lead, followed by heating and carbonizing. The carbonizable material referred to in the present invention refers to a material obtained by heating and carbonizing and / 312 / Invention Specification (Supplement) / 93-02 / 92] 36136 13 200414579 or black heating. Such heating is generally performed at a temperature of 700 ° C or higher, and preferably 8 0 0 to 3 2 0 0 ° C. Therefore, the carbonization treatment referred to in the present invention also includes a black lead treatment, and it is particularly preferable that it is 2000 to 3200 ° C. In addition, at least the surface portion of the black lead referred to in the present invention refers to the whole or a part of the outer surface of the black lead. There are also typical examples of the present invention. The granulated black lead is composed of a plurality of (scaly) black lead. The case of the formed secondary particles refers to the outer surface of the secondary particles or a part thereof. In the case of such secondary particles, the carbonizable material may invade the inside of the secondary particles and carbonize. Of course, the carbon material is sometimes formed inside the black lead monomer. However, in the composite black lead particles of the present invention, it is most suitable that the entire outer surface of the black lead is covered with the carbon material, and a suitable coverage ratio is 50 to 100%. The carbonizable material of the present invention is preferably a mixture of a resin material and tars, and a mass ratio of the resin material to the tars is preferably the resin material / the tars = 5/9 5 to 1 0 0/0 , And more preferably 3 0/7 0 ~ 7 0/30. When the ratio of the resin material is 5% or more, the black discoloration (crystallization) of the carbide layer formed is sufficiently progressed, and the effect of improving the initial charge-discharge efficiency is also increased. It is desirable to use the resin material and the tar in combination to adjust the black lead degree (crystallinity) of the carbon material and maximize the effect of the present invention. The tars referred to in the present invention refer to the precursors of carbon materials such as tar generated during wood distillation, coal tar (coa 1 tar) obtained from coal, and heavy oil produced from petroleum. Polycondensation of raw materials. Specifically, coal-based greening, main mesophase greening (bu 1 kmes 〇phasepitch), petroleum-based asphalt, etc. also include 14 3 12 / Invention Specification (Supplement) / 93-02 / 92136136 200414579 The tar contained in the present invention Class. When these are separately heat-treated at about 3 0 0 ° C, a black lead structure is generated, which may be optically isotropic (i s o t r o p y) or anisotropic (anisotropy). The resin material referred to in the present invention means that at least one kind is selected from a group consisting of a resin itself, a precursor of the resin, and a mixture of synthetic raw materials of the resin, and the precursor of the resin also includes a reaction intermediate and an oligomer (◦ 1 ig. me 1-) or a polymerization intermediate. If a mixture of synthetic raw materials for resin is exemplified, for example, a mixture of monomers, polymerization initiators, and the like may be obtained by stirring and leaving the mixture. In the present invention, as the resin material, at least one kind is preferably selected from the group consisting of a thermosetting resin, a mixture of raw materials of the thermosetting resin, and a precursor of the thermosetting resin. Although carbides obtained by carbonizing thermosetting resins at a high temperature also contain black lead parts that have high average crystallinity equivalent to black lead, they also contain carbon chaotic layer structures. Different from core material black lead. As the thermosetting resin, those having a large amount of residual carbon through heat treatment are preferred, and examples thereof include urea resin, maleic acid resin (ma 1 eic acid), coumar 0 resin (coumar ο neresin), Xylene resin and fluorene acid resin. In the present invention, as the resin material, it is more preferable to use at least one selected from the group consisting of a phenol resin, a mixture of raw materials of a phenol resin, and a precursor of the phenol resin. For more specific examples, the phenolic resin itself can be used (the height of the aldehydes represented by phenols and acetaldehydes with substituents is also high 15 3 丨 2 / Description of the Invention (Supplement) / 93-02 / 92136 丨 36 200414579 degree condensate), the initial condensate of phenols and aldehydes (precursor of phenolic resin), and a mixture of phenols and aldehydes (monomer mixture). The crystallinity of the carbon material constituting the composite black lead particle of the present invention is lower than that of the core material black lead ', and the plane interval d 0 is diffracted by X-rays. 2 is less than 0. 3 4 3 is better. The X-ray diffraction interval d. . 2 If it is less than 0.343 ', the discharge capacity can be further increased' and the adhesion between carbon material and black lead can be improved. The difference between the crystallinity of black lead and the carbon material is d of the carbon material. . 2 d to black ship. . The ratio of 2 is more preferably in the range of 1.0 to 1.0 and less than 1.0. When it is 1.0 or more, the initial charge and discharge efficiency can be further improved, and the adhesiveness of the carbon material can be improved even when it is less than 1.02. (Composite black lead particles) The composite black lead particles of the present invention are shown once again at the interval d of the X-ray diffraction surface. . Composite black lead particles having a carbon material having a lower crystallinity than the black lead at least on the surface portion of the black lead having a thickness of less than 0.3 3 7 nm, and the composite black lead particles having an aspect ratio of 3 or less, the composite 0.5 to 20% by mass of the black lead particles are the carbon material. The Ramanspectrum of the composite black ship particle has a peak intensity (I158〇) of 1580cm_1 and a peak intensity (I1 of 1360cm_1) in the Ramanspectrum. The ratio of 3 6 Q) (I 1 5 8. / I 1 3 6.) Is 0.1 or more to less than 0 · 3 composite black particles, and will be described in more detail. The composite black lead particles are also characterized by an aspect ratio of 3 or less and a shape close to a sphere. The above-mentioned black lead is used as a core material, and a carbon material having lower crystallinity than the black lead exists at least on the surface portion. The R value of Raman spectroscopy can be used to specify the surface crystallinity of the composite black lead particles. The 1 3 6 0 c πΓ 1 spectrum measured by Raman spectroscopy using argon laser (A rg ο η 1 aser) Band Intensity 16 312 / Invention Specification (Supplement) / 93-02 / 92136136 200414579 (Il60) and 1580cm 1 (Ii3Gg / Ii580) (R value) The ratio of the band intensity (Il58G) must be less than 0.1 0. 3. When the R value is less than 0.1 or more than 0.3, the initial charge and discharge efficiency will be lowered, and the R value is particularly preferably from 0.1 to 0.2. In addition, the ratio of the carbon material in the present invention is expressed in terms of carbon content, and the ratio of the carbon material to the composite black lead particles is specified to be in a range of 0.5 to 20% by mass. This ratio corresponds to the granulated black lead occupation. The ratio of composite black lead particles is 80 ~ 99.5%. After the carbonization step, when the carbonizable material is mixed so that the ratio of the granulated black lead to the composite black lead particles is 80 to 99.5%, there are different residual carbons due to the type of carbonizable material selected. The rate cannot be specified in general. However, the granulated black lead is usually mixed with a carbonizable material in an amount of about 1 to 70% by mass. If a more specific example is shown, the case where the carbonizable material is a phenolic resin, etc., it is better to mix about 2 to 50% by mass, and preferably about 20 to 35% by mass. If you refer to it for an appropriate test, you can find Get the right mixing ratio. When the ratio of the carbon material to the composite black lead particles is less than 0.5% by mass, it becomes difficult to completely cover the edge surface of the active black lead, and the initial charge and discharge efficiency decreases. On the other hand, when it exceeds 20% by mass, the relative Ground, the ratio of carbon materials with low discharge capacity increases, and the discharge capacity of composite black lead particles decreases. In addition, when the ratio of the raw materials (thermosetting resin and tar green) used to form the carbon material is large, the particles are easily melted and adhered in the coating step and the subsequent heat treatment step. A portion of the carbon material layer may be cracked or peeled off, causing initial charge-discharge efficiency to decrease. The ratio of the carbon material is particularly preferably 3 to 15% by mass, and more preferably 8 to 12% by mass. In addition, if the ideal physical properties of the composite black lead particles of the present invention are listed, the average particle diameter is 5 to 6 0 " m, the specific surface area is 0, 5 to 10 m 2 / g, and the X-ray is wound around 17 3 12 / Specification of the Invention (Supplement) / 93-02 / 92136 丨 36 200414579 The size of the C-axis direction (upper and d ...) of the crysta 1 1 ite is preferably less than 0.3 3 7 η hi. Within the range of the average particle diameter, other battery characteristics such as discharge capacity, initial charge and discharge efficiency, discharge characteristics, and cycle characteristics are also included. If the surface area is less than 10 m 2 / g, a mixture of a negative electrode material and an adhesive dispersion when forming a negative electrode ) Adhesiveness of viscosity adjustment pen adhesive is improved. When the X-ray diffraction is within a fixed value of Lc, a sufficient discharge capacity can be obtained. Further, in the present invention, since the carbon material is preferably coated, the carbonized layer can also be used to express the composite black portion. (Manufacturing method of composite black lead particles) The present invention also provides a composite black lead particle produced by a mechanical external force to granulate scaly black lead into spherical black lead, and to obtain a composite black 80 to obtain a subsequent carbonization step. 99.5% is the granulated black ship and the step of selecting at least one tree-forming material from the group consisting of the thermosetting resin and the mixture of the precursors of the thermosetting resin in the resulting combination, and the obtained mixture To carry out the carbonization step. When the method for producing the composite black lead particles of the present invention is exemplified, as described above, a mixture of a thermosetting resin-based single resin and a tar is coated on the granulated black lead in advance by a granulation operation or the like as described above, for example, In Mix 3 12 / Invention Manual (Supplement) / 93-02 / 92136136
Lc)為 40n in 以 和寬高比若在規 高，而且急速充 會更為提而。比 合劑糊（負極材 二易，也使依靠 及d 。。2若在規 黑鉛的外表面為 热粒子的該碳材 方法，含有使用 粒子之造粒步 鉛粒子之 粒化黑鉛上混 及熱固性樹脂原 脂材料之可碳 2 0 0 0 〇C〜 3 2 0(TC ，鱗片狀黑船係 成為球狀為佳。 獨或是熱固化性 合機投入被覆材 18 200414579 與造粒化黑鉛，在被覆材的軟化點以上的溫度領域，賦與 強剪切力進行混煉。或是，混合被覆材的溶液或是分散液 與造粒化黑鉛後，乾燥去除溶液或是分散媒的方法等亦被 採用。特別是使熱固化性樹脂以低分子量體（樹脂的前身） 或是單體混合體的形式，在被覆於造粒黑鉛之同時，經由 加熱使之高分子量化為佳。同樣地，在被覆材中含有焦油 類時，在被覆之同時進行焦油類的縮聚是有效的。 在本發明作為被覆材所必須的熱固化性樹脂，以酚醛樹 脂為佳，在該造粒化黑鉛上被覆酚醛樹脂時，以使用酚醛 樹脂前身或是酚醛樹脂的單體含有體為佳。酚醛樹脂前身 或是酚醛樹脂的單體含有體，除了經由加熱熔融或是溶液 化容易以外，可以均勻被覆在造粒黑鉛上。又，在被覆同 時加熱所形成的酚醛樹脂層，具有與造粒化黑鉛堅固黏著 之特徵。 被覆材，可以將複數種組成之物在均質或分散狀態之下 進行被覆，被覆材也可以改變其組成、進行複數次被覆。 例如，可以在該造粒化黑鉛上，被覆苯酚與曱醛所構成的 B分酿樹脂作為第一層後，被覆二甲苯S分（d i m e t h y 1 p h e η ο 1 ; x y 1 e η o 1 ) 與甲酸所構成的二曱g分曱酸樹脂（x y 1 e η ο 1 r e s i n )作為第二層，也可以在該造粒化黑鉛上，被覆瀝青 作為第一層後，被覆酚醛樹脂作為第二層。 被覆材的被覆量，以設定使最後該碳材佔有複合黑鉛粒 子的比率在0 . 5〜2 0質量％為佳。 在該造粒化黑鉛上，被覆被覆材後，或是在被覆處理的 19 312/發明說明書(補件)/93-02/92136136 200414579 同時，以2 0 0〜3 0 0 °C範圍使熱固化性樹脂固化為佳。 在此固化步驟，含在熱固化樹脂和焦油類中的輕揮發 生揮發，通常以花費4小時以上之充分時間升溫為佳 持如此升溫時間，是因為被覆達到完全.，固化可以順 進行，被覆材與造粒化黑錯的黏著性會增力口。 在固化步驟後，依照必要經由粉碎和篩選處理等進 度調整、煅燒為佳。煅燒以在2 0 0 0 °C以上進行為佳， 2 5 0 0〜3 2 0 0 °C更佳，進一步地以2 8 0 0〜3 2 0 0 °C為佳。烺 理以使用艾奇遜（A c h e s ο η )爐為代表的黑鉛化爐，在； 化環境下進行為佳。 在本發明，也提供含有上述某一種複合黑鉛粒子之 材料。 本發明的複合黑鉛粒子，活用其特徵之負極以外用 雖然亦可以轉用為燃料電池隔離板用之導電材料和耐 物用黑鉛等，但是特別適合作為上述鋰離子二次電池 極材料。 亦即，作為本發明之負極材料必要條件，至少含有 的複合黑鉛粒子。因而，本發明的複合黑鉛粒子本身 本發明的負極材料。又，在鋰離子二次電池用途，混 發明複合黑鉛粒子與黏合劑而成的負極合劑，進而添 媒得到的負極合劑糊，進而將其塗布於集電材而成之 等，都是本發明的負極材料範圍。 以下是關於使用本發明的複合黑鉛粒子之鋰離子二 電池負極材料、進而說明鋰離子二次電池。 312/發明說明書(補件)/93-02/92136136 因為 分產 ，維 利地 行粒 燒處 _氧 負極 途， 火 之負 上述 亦是 合本 力口溶 物 次 20 200414579 (鋰離子二次電池用負極材料） 在本發明，亦提供具有上述某一個本發明的複合黑鉛粒 子之鋰離子二次電池用負極材料。 本發明的負極，係將負極材料固化及/或是賦形得到。 該負極的形成，雖可以按照通常的成形方法進行，但若是 能夠得到可以將複合黑鉛粒子的性能充分地發揮，而且對 粉末之賦形性高、化學性、電氣化學性安定的負極之方 法，並沒有任何限制。 製造負、極時，可以使用在複合黑鉛粒子添加黏合劑而成 的負極合劑。作為黏合劑，以使用具有對電解質和電解液 溶媒之化學性安定性、電氣化學性安定性為佳。例如，使 用聚偏氟乙稀（Polyvinylidene fluoride)、聚四氟乙稀 (ρ ο 1 y t e t r a f 1 u〇r 〇 e t h y 1 e n e )等氟系樹脂、聚乙烤、聚乙 烯醇、苯乙稀-丁二烤橡膠、魏甲基纖維素（carboxymethyl cellulose)等，亦可以將此等並用。 黏合劑，通常使用負極合劑全量中1〜2 0質量％左右之量 為佳。 負極合劑層，具體上，可以將使用分級等調整成為適當 粒徑之複合黑鉛粒子，經由與黏合劑混合來調製負極合劑 後，將此負極合劑塗布在通常的集電體之一片或是兩面而 形成。此時，可以使用通常的溶媒，將負極合劑分散在溶 媒中成為糊狀，塗布在集電體上，乾燥時，可以得到負極 合劑層均勻且堅固黏著在集電體上之負極，糊可以使用各 種攪拌器經由攪拌來調製。 21 312/發明說明書(補件)/93-02/92136136 200414579 例如，可以在異丙醇等溶媒中混合本發明的複 子與聚四氟乙烯等氟系樹脂粉末，在混煉後塗布 合劑層。亦可以將本發明的複合黑雜粒子和聚偏 氟系樹脂粉末或是叛甲基纖維素（c a r b ο X y m e t h y 1 c e 1 1 u 1〇s e )等水溶性黏接劑與N -甲基口比口各烧酉同（1 pyrrol idone) ^ 二甲基曱 月安（dimethylformami 水、醇等溶媒混合作成淤漿後，塗布形成負極合 將由本發明的複合黑鉛粒子與黏合劑所構成的 劑塗布在集電體上時之塗布厚度，以1 0〜3 0 0 // m 形成負極合劑層後，若施行壓力機加壓等加壓 以使負極合劑層與集電體之黏著強度更為提高。 在本發明的鋰離子二次電池，在負極所使用集 狀並沒有特別限定，可以使用箔狀、或是金屬網 展開金屬（e X p a n d in e t a 1 )等網狀物。作為集電材 可以舉出銅、不鏽鋼、鎳等，集電材的厚度，箔 5〜20# m左右為適合。 本發明進一步提供使用上述負極材料之鋰離子 池。 (鋰離子二次電池） 鋰離子二次電池通常是以負極材料、正極材料 電解質作為主要構成要素，正極材料及負極材料 離子的支持體，電池機構係充電時鋰離子摻混入 放電時由負、極脫摻混。 本發明的鋰離子二次電池，除了使用含有本發 312/發明說明書(補件)/93-02/92丨36136 合黑鉛粒 形成負極 氟乙烯等 Μ - m e t h y 1 d e )或是 劑層。 負極合 為適當。 黏著，可 電體的形 (mesh)、 ，例如， 狀時以 二次電 及非水系 是各自鋰 負極中， 明的複合 22 200414579 黑鉛粒子作為負極材料以外，沒有特別的限定，關於其他 的構成要素，依照一般鋰離子二次電池的要素。 (正極材料） 本發明的鋰離子二次電池使用鋰化合物作為正極材料 (正極活性物質），選擇可以摻混入/脫摻混充足量的鋰為 佳，例如含有链之過鍍金屬氧化物、過鑛金屬硫屬 (chalcogen)化物、飢（vanadium)氧化物及其Li化合物等 含鋰化合物，一般式以MxM〇6S8-y (式中X為0SXS4，Y 為0 S Y S 1範圍的數值，Μ表示過渡金屬等金屬）表示之謝 佛雷相（C h e ν r e 1 p h a s e )化合物、活性炭、活性碳纖維等， 飢氧化物係以V 2 0 5、V 6 0 1 3、V 2 0 4、V 3 0 8等表示。 含有鋰之過鍍金屬氧化物係鋰與過渡金屬的複合氧化 物，將鋰與二種類以上的過渡金屬固熔而成之物亦可，複 合氧化物可以單獨使用，亦可以組合二種類以上使用。含 有鋰之過鍍金屬氧化物，具體上，係以L i Μ ( 1 ) I - X Μ ( 2 ) X 0 2 (式 中X為0SXS4範圍之數值，Μ(1)、Μ(2)為至少一種過渡 金屬元素所構成）或是LiM(l)丨-yM(2)y〇4(式中Υ為0$Υ€1 範圍之數值，Μ ( 1 )、Μ ( 2 )為至少一種過渡金屬元素所構成） 表示。 式中，Μ(1)、Μ(2)所代表的過渡金屬元素為Co、Ni、Mn、 Cr、Ti、V、Fe、Zn、Al、 In、Sn 等，以 C〇、Fe、Mn、Ti、 Cr 、 V 、 A1 為佳。 又，含有裡之過鍍金屬氧化物，例如，可以將過錢金屬 氧化物或是鹽類作為出發原料，按照所希望之金屬氧化物 23 3 12/發明說明書(補件)/93-02/92136丨36 200414579 之組成混合此等出發原料，在氧氣存在環境下以6 0 0 °C 〜1 Ο Ο 0 °c之溫度範圍煅燒得到。又，出發原料未限定在氧 化物或是鹽類，氫氧化物亦可。 在本發明的鋰離子二次電池，正極活性物質可以單獨使 用上述鋰化合物，亦可以二種類以上並用，又，正極材料 中，亦可以添加碳酸鋰等碳酸鹼鹽。 正極材料，例如，可以經由在集電體的一面或兩面塗布 正極合劑（由上述鋰化合物與黏合劑以及為了賦與電極導 電性之導電劑所構成）來形成正極合劑層而得到。作為黏 合劑，可以使用任何一者在負極所例示之物。作為導電 劑，可以使用黑錯和炭黑（c a r b ο n b 1 a c k )等碳材料。 正極材料亦與負極材料同樣，使正極合劑分散在溶媒中 成為糊狀，將此糊狀之正極合劑塗布在集電體上，可以經 由乾燥得到正極合劑層，亦可以在形成正極合劑層後，進 一步以壓力機加壓等加壓黏著，如此可以使正極合劑層均 勻且堅固地黏著在集電體上。 集電體的形狀並沒有特別限定，可以使用箱狀、或是金 屬網（m e s h )、展開金屬（e X p a n d ni e t a 1 )等網狀物。例如， 作為集電材，可以舉出鋁箔、不鏽鋼箔、鎳箔等，其厚度 以10〜40//U1為適合。 (非水電解質） 作為本發明的鋰離子二次電池所使用之非水電解質，係 在通常非水電解液所使用的電解質鹽，可以舉出的有 LiPF(;、L i BF4 > Li AsFe > LiCICh、Li B(C6H5) > LiCl > LiBr、 24 3 12/發明說明書(補件)/93-02/92136136 200414579Lc) is 40n in and if the aspect ratio is high, and the rapid charge will be more mention. Compared with the mixture paste (negative electrode material, it also depends on d. 2) If the carbon material method in which the outer surface of black lead is hot particles, the granulated black lead containing lead particles is granulated using particles. Carbon and thermosetting resin raw material can be carbon 2 0 0 0 ~ 3 2 0 (TC, scaly black ship system to become spherical. It is better to put coating material 18 200414579 and granulation by thermosetting machine. Black lead is kneaded with a strong shear force in a temperature range above the softening point of the coating material. Alternatively, the solution or dispersion of the coating material is mixed with granulated black lead, and the solution is dried to remove or disperse. It is also used as a medium method. In particular, the thermosetting resin is coated with granulated black lead in the form of a low molecular weight body (precursor of the resin) or a monomer mixture, and the polymer is quantified by heating. Similarly, when tars are contained in the coating material, it is effective to perform polycondensation of the tars at the same time as coating. In the present invention, the thermosetting resin necessary for the coating material is preferably a phenol resin. Coated phenol on granulated black lead In the case of resins, it is preferable to use a phenolic resin precursor or a monomer containing body of the phenolic resin. The phenolic resin precursor or the monomer containing body of the phenolic resin can be uniformly coated and granulated in addition to being easily melted by heating or solution. Black lead. In addition, the phenolic resin layer formed by heating while coating has the characteristics of strong adhesion to granulated black lead. The coating material can be coated with a plurality of components in a homogeneous or dispersed state. The material can also be changed in composition and coated several times. For example, the granulated black lead can be coated with a B fraction resin made of phenol and formaldehyde as the first layer and then coated with xylene S fraction (dimethy 1 phe η ο 1; xy 1 e η o 1) and formic acid glycid acid resin (xy 1 e η ο 1 resin) as the second layer may be coated on the granulated black lead After the bitumen is used as the first layer, the phenolic resin is used as the second layer. The coating amount of the coating material is set such that the ratio of the carbon material to the composite black lead particles is preferably 0.5 to 20% by mass. Granulated black lead, after covering the coating material, or after coating treatment 19 312 / Invention Specification (Supplement) / 93-02 / 92136136 200414579 At the same time, the thermosetting property is made in the range of 2 0 ~ 3 0 0 ° C The resin is preferably cured. In this curing step, the volatilization contained in the thermosetting resin and tars will volatilize, usually it takes 4 hours or more to heat up, it is better to hold this temperature up time, because the coating is complete. Curing It can be carried out smoothly, and the adhesion between the coating material and the granulated black particles will be strengthened. After the curing step, it is better to adjust and calcinate through the progress of pulverization and screening as necessary. The calcination should be above 2000 ° C. It is better to proceed, 2 500 to 3 2 0 ° C is more preferable, and further preferably 2 8 0 to 3 2 0 ° C.烺 The black lead smelting furnace, represented by the use of an Acheson (A c h e s ο η) furnace, is best carried out in a chemical environment. The present invention also provides a material containing one of the composite black lead particles. The composite black lead particles of the present invention can be used for other purposes than the negative electrode. Although the composite black lead particles can also be used as conductive materials for fuel cell separators and black lead for refractory materials, they are particularly suitable as the aforementioned lithium ion secondary battery electrode materials. That is, as a requirement for the negative electrode material of the present invention, at least the composite black lead particles are contained. Therefore, the composite black lead particle of the present invention itself is the negative electrode material of the present invention. In addition, in the application of lithium ion secondary batteries, a negative electrode mixture in which composite black lead particles and a binder are invented, and a negative electrode mixture paste obtained by adding a medium, and then applying the negative electrode mixture paste to a current collector are all the invention. Range of negative electrode materials. The following is a description of a lithium ion secondary battery negative electrode material using the composite black lead particles of the present invention, and further a lithium ion secondary battery. 312 / Invention Manual (Supplements) / 93-02 / 92136136 Because of the production division, Villidi has a grain burning place _ oxygen negative way, the negative of the fire is also the above-mentioned solution. 20 200414579 (secondary lithium ion Negative electrode material for batteries) In the present invention, there is also provided a negative electrode material for a lithium ion secondary battery having the composite black lead particle of the present invention. The negative electrode of the present invention is obtained by curing and / or shaping a negative electrode material. Although the formation of the negative electrode can be performed according to a general molding method, if a negative electrode that can fully exhibit the performance of the composite black lead particles and has a high forming property to the powder, and has stable chemical and electrochemical properties can be obtained. And there are no restrictions. When manufacturing a negative electrode or a negative electrode, a negative electrode mixture obtained by adding a binder to the composite black lead particles can be used. As the binder, it is preferable to use chemical stability and electrochemical stability of the electrolyte and the electrolyte solvent. For example, fluorine-based resins such as polyvinylidene fluoride (polyvinylidene fluoride) and polytetrafluoroethylene (ρ ο 1 ytetraf 1 u〇r 〇ethy 1 ene), polyethylene baking, polyvinyl alcohol, and styrene-butylene Two-roasted rubber, carboxymethyl cellulose, etc. can also be used in combination. The binder is usually used in an amount of about 1 to 20% by mass of the total amount of the negative electrode mixture. Specifically, the negative electrode mixture layer can be composite black lead particles adjusted to a suitable particle size by classification or the like, and mixed with a binder to prepare the negative electrode mixture, and then apply the negative electrode mixture to one or both sides of a normal current collector. And formed. At this time, a normal solvent can be used, and the negative electrode mixture is dispersed in the solvent to form a paste, and the current collector is coated on the current collector. When dried, the negative electrode mixture layer can be uniformly and firmly adhered to the current collector. The paste can be used Various stirrers are prepared by stirring. 21 312 / Invention specification (Supplement) / 93-02 / 92136136 200414579 For example, the compound of the present invention and a fluorine resin powder such as polytetrafluoroethylene can be mixed in a solvent such as isopropanol, and a mixture layer can be applied after kneading. . The water-soluble adhesives such as the composite black particles and the polyvinylidene fluoride resin powder of the present invention, or methyl cellulose (carb ο X ymethy 1 ce 1 1 u 1〇se) can also be used with the N-methyl port. 1 pyrrol idone ^ dimethylformami water, alcohol and other solvents are mixed to form a slurry, and then coated to form a negative electrode. The agent composed of the composite black lead particles of the present invention and a binder The coating thickness when coating on the current collector, after forming the negative electrode mixture layer at 10 ~ 3 0 0 // m, if pressurizing by a press or the like, the adhesion strength between the negative electrode mixture layer and the current collector is further increased. In the lithium ion secondary battery of the present invention, the collector used for the negative electrode is not particularly limited, and a foil or a metal mesh expanded metal (e X pand in eta 1) can be used. As a current collector Examples include copper, stainless steel, and nickel. The thickness of the current collector is about 5 to 20 # m. The present invention further provides a lithium ion cell using the above negative electrode material. (Lithium ion secondary battery) Lithium ion secondary battery Usually with negative electrode material, The positive electrode material electrolyte is the main constituent element, the positive electrode material and the negative electrode material support, the battery mechanism is charged when lithium ions are mixed into the discharge when the negative and de-doped. In addition to using the lithium ion secondary battery of the present invention Hair 312 / Invention Specification (Supplement) / 93-02 / 92 丨 36136 combined with black lead particles to form negative electrode fluoroethylene and other M-methy 1 de) or agent layer. The negative electrode is appropriate. The shape of the adherent, electrified body, for example, secondary lithium and non-aqueous lithium ion negative electrodes in the shape, the composite 22 200414579 black lead particles as the negative electrode material is not particularly limited, and other The constituent elements are those of a general lithium ion secondary battery. (Positive electrode material) The lithium ion secondary battery of the present invention uses a lithium compound as a positive electrode material (positive electrode active material), and it is preferable to select a sufficient amount of lithium that can be doped / dedoped. Lithium-containing compounds such as chalcogen compounds, vanadium oxides, and Li compounds of the mineral metals. The general formula is MxM0S6-y (where X is 0SXS4, Y is a value in the range of 0 SYS 1, and M represents C he ν re 1 phase compounds, activated carbon, activated carbon fibers, etc., which are represented by metals such as transition metals. The oxides are V 2 0 5, V 6 0 1 3, V 2 0 4, V 3 0 8 And so on. A composite oxide of lithium-containing overplating metal oxide-based lithium and a transition metal may be obtained by solid-melting lithium with two or more types of transition metals. The composite oxide may be used alone or in combination of two or more types. . The lithium-containing overplated metal oxide is specifically L i Μ (1) I-X Μ (2) X 0 2 (where X is a value in the range of OSXS4, and M (1) and M (2) are Consisting of at least one transition metal element) or LiM (l) 丨 -yM (2) y〇4 (where Υ is a value in the range of 0 $ Υ € 1, and M (1), M (2) are at least one transition Metal elements). In the formula, the transition metal elements represented by M (1) and M (2) are Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn, etc., with Co, Fe, Mn, Ti, Cr, V, A1 are preferred. In addition, if the over-plated metal oxide is contained, for example, a metal oxide or a salt can be used as a starting material, according to the desired metal oxide 23 3 12 / Invention Specification (Supplement) / 93-02 / The composition of 92136 丨 36 200414579 is obtained by mixing these starting materials and calcining it in the temperature range of 6 0 ° C ~ 1 0 0 0 ° c in the presence of oxygen. The starting materials are not limited to oxides and salts, and hydroxides may be used. In the lithium ion secondary battery of the present invention, the above-mentioned lithium compound may be used alone as a positive electrode active material, or two or more types may be used in combination. Alternatively, a carbonate such as lithium carbonate may be added to the positive electrode material. The positive electrode material can be obtained by, for example, applying a positive electrode mixture (consisting of the lithium compound and a binder and a conductive agent for imparting electrode conductivity) to one or both sides of a current collector to form a positive electrode mixture layer. As the binder, any of those exemplified for the negative electrode can be used. As the conductive agent, carbon materials such as black coke and carbon black (c a r b ο n b 1 a c k) can be used. The positive electrode material is the same as the negative electrode material. The positive electrode mixture is dispersed in a solvent to form a paste, and the pasty positive electrode mixture is coated on a current collector. The positive electrode mixture layer can be obtained by drying. After forming the positive electrode mixture layer, Further, pressurization and adhesion with a press machine or the like can make the positive electrode mixture layer uniformly and firmly adhere to the current collector. The shape of the current collector is not particularly limited, and a box-like shape, a metal mesh (mesh), or a expanded metal (eXp a n d ni e t a 1) may be used. For example, examples of the current collector include aluminum foil, stainless steel foil, and nickel foil. The thickness is preferably 10 to 40 // U1. (Non-aqueous electrolyte) The non-aqueous electrolyte used in the lithium ion secondary battery of the present invention is an electrolyte salt used in a general non-aqueous electrolyte, and examples thereof include LiPF (;, Li BF4 > Li AsFe > LiCICh, Li B (C6H5) > LiCl > LiBr, 24 3 12 / Invention Specification (Supplement) / 93-02 / 92136136 200414579
LiCF3S〇3、 LiCH3S〇3、 LiN(CF3S〇2)2、 LiC(CF3S〇2)3、 LiN(CF3CH2〇S〇2)2、LiN(CF3CF2〇S〇2)2、 LiN(HCF2CF‘2CH2〇S〇2)2、LiN((CF3)2CHOS〇2)2、 LiB[(CGH3((CF3)2)4、LiAlCh、LiSiF6 等鋰鹽。從氧化安 定性的觀點，特別是以L i P F G、L i B F 4等為佳。 電解液中的電解質鹽濃度，以0 . 1〜0 . 5莫耳/公升為佳， 0 . 5〜3 . 0莫耳/公升更佳。 非水電解質，可以是液狀的非水電解質，亦可以是固體 電解質或是凝膠電解質等之高分子電解質。前者的情況， 非水電解質電池的構成是作為所謂的鋰離子電池，後者的 情況，非水電解質電池的構成是作為高分子固體電解質、 高分子凝膠電解質電池等高分子電解質電池。 液狀的非水電解質的情況，作為溶媒可以使用碳酸乙烯 Si (ethylene carbonate)、碳酉曼丙稀酉旨（propylene carbonate)、 ·碳 S复二曱 6旨（dimethyl carbonate)、碳酉复二 乙酯（diethyl carbonate)等碳酸酯、1，1_或是 1,2 -二甲 氧基乙烧（1， 1-orl， 2-dimethoxyethane) 、 1， 2-二乙氧基 乙烧（1，2 - diethoxyethane)、四氫口夫口南 (tetrahydrofuran) 、 2-曱基四氫口夫喃 (2-methyl-tetrahydrofuran) 、 γ -丁 内醋 (7 —butyrolactone) 、 1，3 -二氧^4 口夫口南 (1，3- di 〇x〇- fur an)、4 -曱基-1, 3-二氧代 σ夫喃 (4-methyl-l，3-diox〇-fur an)、茴香醚（anisole) ' 二乙 s 迷（diethyl ether)等 、環 丁石風（sulfolane)、甲基環丁 25 3丨2/發明說明書(補件)/93-02/92136136 200414579 石風（methyl-sulfolane)等硫 6迷（thioether)、乙腈 (acetonitrile)、氯腈（chloronit rile)、丙腈 (p r〇pi〇nitrile)等月惫（nitrile)、石朋酸三曱酯、原石夕酸乙 6a (tetraethyl ortho-silicate)、硝基甲烧 (nitromethane) 、 N，N-二曱基甲酿胺 (dimethyl-formamide) 、 N_ 曱基 σ比略：)：完酉同（N_methyl pyrolidone)、乙酸乙醋（ethyl acetate)、三甲基原曱酸 Θ旨（trim ethyl ortho-formate)、石肖基苯（nitrobenzene)、 苯 S& 氯（benzol chloride)、苯酸溴（benzol bromide)、 四氫化 口塞吩（tetrahydrothiophene)、二曱亞石風（dimethyl sulfoxide)、3 -曱基-2-"惡唑烷酮（3-methyl-2-oxazolidone)、乙二醇（ethylene glycol)、硫化物 (sulfide)、二甲基硫化物（dimethyl sulfide)等非質子 性有機溶媒。 使用非水電解質作為高分子固體電解質、高分子凝膠電 解質等之高分子電解質時，係使用以可塑劑（非水電解液） 凝膠化而成的高分子作為基質（m a t r i X )。作為構成該基質 的兩分子’以聚氧化乙稀（polyethyleneoxide)和其交聯 體等醚系南分子、聚曱基内焊酸酯（p〇ly methacrylate)系 向分子化合物、聚丙稀酸S旨（p 〇 1 y a c r y 1 a t e )等丙稀酸S旨系 南分子化合物、聚偏氟乙烯（polyvinylidene fluoride)(PVDF)和偏氟乙稀（vinyiidene fluoride)-六 氟丙烯（h e x a f 1 u o r o p r o p y丨e n e )共聚合體等氟系高分子化 合物等為特佳。 26 312/發明說明書(補件)/93-02/92136】36 200414579 上述高分子固體電解質或是高分子凝膠電解質是使用 可塑材配合而成，作為可塑材，可以使用上述的電解質鹽 和非水溶媒。在高分子凝膠電解質的情況，在可塑劑非水 電解液中之電解質鹽濃度，以0 . 1〜0 . 5莫耳/公升為佳， 0 . 5〜2 . 0莫耳/公升更佳。 製造固體電解質並沒有特別的限制，例如，可以舉出的 有混合形成基質（m a t r i X )之高分子化合物、經鹽及非水溶 媒（可塑劑）等，加熱使高分子化合物熔融的方法，在有機 溶劑中將鋰鹽及非水溶媒（可塑劑）溶解後，將有機溶劑蒸 發的方法，以及混合構成高分子電解質原料之聚合用單 體、鋰鹽及非水溶媒（可塑劑）等，對混合物照射紫外線、 電子線或是分子線等來形成聚合物之方法等。 又，上述固體電解質中的非水溶媒（可塑劑）之添加量， 以1 0〜9 0質量％為佳，3 0〜8 0質量％更佳。未滿1 0質量％時， 導電率降低，超過9 0質量％時，機械強度降低使成膜變為 困難。 (隔離板） 在本發明的鋰離子二次電池可以使用隔離板。隔離板的 材質沒有特別的限定，例如，可以例示的有織布、不織布、 合成樹脂製微多孔質膜等，特別是以合成樹脂製微多孔膜 最為適合，不過從厚度、膜強度、膜阻抗等觀點，其中， 以聚稀烴（ρ ο 1 y ο 1 e f i n e )系多孔質膜為適合。具體上，有 聚乙烯及聚丙烯製微多孔質膜，或是將此等複合而成之微 多孔質膜。 27 3丨2/發明說明書(補件)/93-02/92136136 200414579 又，亦可以使用未使用隔離板之凝膠電解質。 使用凝膠電解質之二次電池，是將含有上述複合黑鉛粒 子之負極材料和、正極材料及凝膠電解質，例如以負極材 料、凝膠電解質、正極材料之順序層疊，收容在電池的外 裝材内所構成的。亦可以進而在負極材料與正極材料的外 側配置電解質。 此外，本發明的鋰離子二次電池的構造並沒有特別限 制，關於其形狀、形態沒有特別的限定，依照其用途、裝 載機器、要求充放電容量，可為圓筒型、角型、硬幣形、 鈕釦型等任何一種形狀或是形態。為了得到更高安全性之 高密閉性非水電解液電池，在過充電等異常時，最好具備 能夠感應察知電池内壓上升而將電流隔斷之機構。在高分 子固體電解質電池和高分子凝膠電池的情況，裝入層壓薄 膜之構造亦可。 (實施例） 接著經由實施例來說明本發明，但本發明不限定在此等 實施例。 又，以下之實施例及比較例，係將複合黑鉛粒子製造成 如圖1所示構成之評價用鈕釦型二次電池而進行評價。但 是，實際電池可以用本發明的概念作為基礎，依照眾所知 道方法製造。關於該評價用電池，以負極表示作用極、正 極來表示對電極（counter electrode)0 〈負極合劑糊的調製〉 在水中添加複合黑鉛粒子9 8質量％、作為黏合劑之苯乙 28 3 12/發明說明書(補件)/93-02/92136136 200414579 烯-丁二烯橡膠1質量％、羧曱基纖維素1質量％之比率並 調製成淤漿狀負極合劑糊。 〈負極材料的製造〉 在銅箔（集電材）上，以均勻厚度塗布上述負極合劑糊， 進而在真空中以9 0 °C加熱使溶劑揮發而乾燥。接著，經由 滾筒壓力機對塗布於銅箔上的負極合劑加壓，進而經由與 銅箔一起貫穿使成為直徑1 5 . 5 m hi的圓形狀，製成由集電 體7 b (由銅箔所構成）黏著負極合劑層所構成的負極2。 〈正極材料的製造〉 將鋰金屬箔緊壓在鎳網上，貫穿使成為直徑1 5 . 5 m m的 圓柱狀，製成由集電體7 a (由鎳網所構成）與黏著於該集電 體之鋰金屬fg所構成的正極4。 〈電解質〉 在碳酸乙烯酯3 3 v〇1 %及碳酸乙基曱基酯6 7 v 〇 1%比率之 混合溶媒，使L i P F 6以1 m ο 1 / d m3的濃度溶解在其中，來調 製成非水電解液。在聚烯烴多孔質體上含浸所得到的非水 電解液，製成含浸有電解液之隔離板5。 〈評價用電池的製造〉 製造具有圖1構造之鈕釦型二次電池作為評價電池。 首先，在黏著於集電體7 b之負極（作用電極）與黏著於 集電體7 a之正極（對電極）之間，夾住含浸有電解質溶液 的隔離板5而層疊，其後，使負極集電體7b側在外裝杯1 内，使正極集電體7a側在外裝罐3内，如此收容，將外 裝杯1與外裝罐3合起，此時，外裝杯1與外裝罐3的周 29 3 12/發明說明書(補件)/93-02/92136136 200414579 邊部置入絕緣墊片6、填隙縫來密閉兩周邊部。 關於經由上述製作得到的評價電池，是在2 5 °C的溫度下 進行如下述之充放電試驗。 關於經由上述製造得到的評價用電池，是在2 5 °C的溫度 進行下述充放電試驗。 〈充放電試驗〉 以0 . 9 m A的電流值進行定電流充電至電路電壓達到0 hi V 為止。接著，在電路電壓達到OmV時，切換成定電壓充電， 進而繼續充電至電流值為2 0 // A，其後停止1 2 0分鐘。 接著以0 . 9 m A的電流值進行定電流放電至電路電壓達到 2 . 5 V為止，由此第1循環通電量求得充電容量和放電容 量，由下式計算初期充放電效率。 初期充放電效率(％)二 (第1循環的放電容量)^ ^ (第1循環的充電容量） 又，此試驗係在將鋰離子摻混入複合黑鉛粒子中之步驟 充電，在鋰離子從複合黑鉛粒子脫摻混之步驟放電。 所測定之複合黑船粒子平均1 g之放電容量（m A h / g )和初 期充放電效率（％)之值等電池特性如表2所顯示。 如表2所示般，於負極中使用了本發明的複合黑鉛粒子 之鋰離子二次電池顯示大的放電容量，而且具有高的初期 充放電效率。 接著是第2循環，在和第1循環同樣充電後，以2 0 m A 的電流值進行定電流放電至電路電壓達到2，5 V為止，此 時由第1循環之放電容量和第2循環的放電容量，依照下 30 312/發明說明書(補件)/93-02/92136136 200414579 式來評價急速放電效率。 急速放電效率(％)= (第2循環的放電容量) (第1循環的放電容量)LiCF3S〇3, LiCH3S〇3, LiN (CF3S〇2) 2, LiC (CF3S〇2) 3, LiN (CF3CH2〇S〇2) 2, LiN (CF3CF2〇S〇2) 2, LiN (HCF2CF'2CH2. S〇2) 2, LiN ((CF3) 2CHOS〇2) 2, LiB [(CGH3 ((CF3) 2) 4, LiAlCh, LiSiF6, and other lithium salts. From the viewpoint of oxidation stability, especially Li PFG, L i BF 4 is preferred. The electrolyte salt concentration in the electrolyte is preferably from 0.1 to 0.5 mol / liter, and more preferably from 0.5 to 3.0 mol / liter. Non-aqueous electrolyte, can It is a liquid non-aqueous electrolyte, and it can also be a solid electrolyte or a polymer electrolyte such as a gel electrolyte. In the former case, the non-aqueous electrolyte battery is constituted as a so-called lithium ion battery, and in the latter case, the non-aqueous electrolyte battery. The structure is used as a polymer electrolyte battery such as a polymer solid electrolyte, a polymer gel electrolyte battery, and the like. In the case of a liquid nonaqueous electrolyte, as a solvent, ethylene carbonate (ethylene carbonate), carbohydrate, etc. can be used. propylene carbonate), carbon dimethyl carbonate 6 purpose (dimethyl carbonate), carbon ethyl biscarbonate (diethyl carbonate), etc. Carbonate, 1,1_ or 1,2-dimethoxyethane (1,2-diethoxyethane), 1,2-diethoxyethane, 1,2 Tetrahydrofuran, 2-methyl-tetrahydrofuran, 7-butyrolactone, 1,3 -dioxy ^ 4 1,3-dioxo-fur an), 4-methyl-1,3-dioxo-furan, anisole '' Diethyl ether, diethyl ether, sulfolane, methylcyclobutane 25 3 丨 2 / Instruction of the Invention (Supplement) / 93-02 / 92136136 200414579 methyl-sulfolane, and other sulfur 6 Nitroether, acetonitrile, chloronitrile, propionitrile, etc., nitrile, tris (3,3,3) -tetramethyl ortho-silicate, tetraethyl ortho-silicate ), Nitromethane, N, N-dimethyl-formamide, N_fluorenyl σ ratio :): N_methyl pyrolidone, ethyl acetate , Trimethyl orthophosphoric acid Θ purpose (trim ethy l ortho-formate), nitrobenzene, benzene S & chloride (benzol chloride), benzol bromide, tetrahydrothiophene, dimethyl sulfoxide, 3- Amino-2- " 3-methyl-2-oxazolidone, ethylene glycol, sulfide, dimethyl sulfide and other aprotic organic solvents . When a non-aqueous electrolyte is used as a polymer solid electrolyte, polymer gel electrolyte, or other polymer electrolyte, a polymer gelled with a plasticizer (non-aqueous electrolyte) is used as a matrix (m a t r X). As the two molecules constituting the matrix, an ether-based molecule such as polyethylene oxide and a crosslinked body thereof, a polymethyl methacrylate-based molecular compound, and a polyacrylic acid S are used. (P 〇1 yacry 1 ate) and other acrylic acid S are molecular compounds, polyvinylidene fluoride (PVDF), and vinylidene fluoride (hexaf 1 uoropropy 丨 ene) Particularly preferred are fluorine-based polymer compounds such as copolymers. 26 312 / Invention Manual (Supplement) / 93-02 / 92136] 36 200414579 The above polymer solid electrolyte or polymer gel electrolyte is made by using a plastic material. As a plastic material, the above-mentioned electrolyte salt and non-electrolyte can be used. Water solvent. In the case of polymer gel electrolytes, the electrolyte salt concentration in the plasticizer non-aqueous electrolyte is preferably from 0.1 to 0.5 mol / liter, and more preferably from 0.5 to 2.0 mol / liter. . There are no particular restrictions on the production of solid electrolytes. For example, there can be mentioned a method of mixing a polymer compound forming a matrix (matri X), a method of heating a polymer compound with a salt and a non-aqueous solvent (plasticizer), and the like. A method of dissolving a lithium salt and a non-aqueous solvent (plasticizer) in an organic solvent, and then evaporating the organic solvent, and mixing a polymerization monomer, a lithium salt, and a non-aqueous solvent (plasticizer) constituting a polymer electrolyte raw material. A method of forming a polymer by irradiating a mixture with ultraviolet rays, electron rays, or molecular rays. The addition amount of the non-aqueous solvent (plasticizer) in the solid electrolyte is preferably 10 to 90% by mass, and more preferably 30 to 80% by mass. When the content is less than 10% by mass, the electrical conductivity is lowered. When the content is more than 90% by mass, the mechanical strength is lowered and it becomes difficult to form a film. (Separator) A separator can be used for the lithium ion secondary battery of the present invention. The material of the separator is not particularly limited. Examples include woven fabrics, non-woven fabrics, and microporous membranes made of synthetic resin. Particularly, microporous membranes made of synthetic resin are most suitable. However, the thickness, membrane strength, and membrane impedance are suitable. Among other viewpoints, among them, a polyolefin (ρ ο 1 y ο 1 efine) -based porous film is suitable. Specifically, there are microporous films made of polyethylene and polypropylene, or microporous films formed by compounding these. 27 3 丨 2 / Invention Specification (Supplement) / 93-02 / 92136136 200414579 In addition, a gel electrolyte without a separator can also be used. A secondary battery using a gel electrolyte is a negative electrode material containing the composite black lead particles, a positive electrode material, and a gel electrolyte, which are stacked in the order of a negative electrode material, a gel electrolyte, and a positive electrode material, for example, and are housed in the exterior of the battery. Made of wood. An electrolyte may be further disposed outside the negative electrode material and the positive electrode material. In addition, the structure of the lithium ion secondary battery of the present invention is not particularly limited, and its shape and form are not particularly limited. It can be cylindrical, angular, or coin-shaped according to its use, loading equipment, and required charge and discharge capacity. , Button type and any other shape or form. In order to obtain a highly-sealed non-aqueous electrolyte battery with higher safety, it is desirable to have a mechanism that can detect the rise in the internal pressure of the battery and block the current when abnormalities such as overcharge occur. In the case of high-molecular solid-electrolyte batteries and polymer gel batteries, a laminated film structure may be used. (Examples) Next, the present invention will be described by way of examples, but the present invention is not limited to these examples. The following examples and comparative examples were evaluated by producing composite black lead particles into an evaluation button-type secondary battery having a structure as shown in FIG. 1. However, actual batteries can be manufactured using well-known methods based on the concept of the present invention. Regarding the battery for evaluation, a negative electrode is a working electrode and a positive electrode is a counter electrode. 0 <Preparation of a negative electrode mixture paste> 98% by mass of composite black lead particles were added to water, and styrene was used as a binder. 28 3 12 / Invention specification (Supplement) / 93-02 / 92136136 200414579 A ratio of 1% by mass of olefin-butadiene rubber and 1% by mass of carboxymethyl cellulose and prepared into a slurry-like negative electrode mixture paste. <Production of Negative Electrode Material> The above-mentioned negative electrode mixture paste was applied to a copper foil (current collector) with a uniform thickness, and the solvent was evaporated and dried by heating at 90 ° C in a vacuum. Next, the negative electrode mixture coated on the copper foil was pressurized by a roller press, and then passed through the copper foil to a circular shape having a diameter of 15.5 m hi. The current collector 7 b (made of copper foil (Composition) A negative electrode 2 composed of a negative electrode mixture layer adhered. <Manufacturing of a positive electrode material> A lithium metal foil was pressed tightly on a nickel mesh and penetrated into a cylindrical shape having a diameter of 15.5 mm to form a current collector 7 a (consisting of a nickel mesh) and adhered to the current collector. A positive electrode 4 composed of a lithium metal fg of an electric body. <Electrolyte> In a mixed solvent with a ratio of 3 3 vO1% of ethylene carbonate and 67 v 0% of ethyl fluorenyl carbonate, Li PF 6 is dissolved therein at a concentration of 1 m ο 1 / d m3, To prepare a non-aqueous electrolyte. The porous non-aqueous electrolyte obtained was impregnated with the porous polyolefin body to prepare a separator 5 impregnated with the electrolytic solution. <Production of Evaluation Battery> A button-type secondary battery having a structure shown in FIG. 1 was produced as an evaluation battery. First, between a negative electrode (active electrode) adhered to the current collector 7 b and a positive electrode (counter electrode) adhered to the current collector 7 a, the separator 5 impregnated with the electrolyte solution is laminated, and thereafter, The side of the negative electrode current collector 7b is inside the exterior cup 1, and the side of the positive electrode current collector 7a is inside the exterior tank 3, so that it is accommodated, and the exterior cup 1 and the exterior tank 3 are combined. At this time, the exterior cup 1 and the exterior Week 29 3 of canning 3 12 / Invention specification (Supplement) / 93-02 / 92136136 200414579 Insert insulation gasket 6 and fill gaps at the sides to seal the two peripheral parts. The evaluation battery obtained as described above was subjected to a charge-discharge test as described below at a temperature of 25 ° C. The battery for evaluation obtained through the above-mentioned production was subjected to the following charge-discharge test at a temperature of 25 ° C. <Charge and Discharge Test> Charge at a constant current with a current value of 0.9 m A until the circuit voltage reaches 0 hi V. Then, when the circuit voltage reaches OmV, it switches to constant voltage charging, and then continues to charge until the current value is 2 0 // A, and then stops for 120 minutes. Then, discharge at a constant current with a current value of 0.9 m A until the circuit voltage reaches 2.5 V. From the first cycle of current flow, the charge capacity and discharge capacity are obtained, and the initial charge and discharge efficiency is calculated from the following formula. Initial charge and discharge efficiency (%) 2 (discharge capacity in the first cycle) ^ ^ (charge capacity in the first cycle) In addition, this test is charged in the step of mixing lithium ions into composite black lead particles. The step of demixing the composite black lead particles is discharged. The measured battery characteristics, such as the average discharge capacity (m A h / g) of the composite black ship particles and the initial charge and discharge efficiency (%), are shown in Table 2. As shown in Table 2, a lithium ion secondary battery using the composite black lead particles of the present invention in a negative electrode shows a large discharge capacity and has a high initial charge-discharge efficiency. Next is the second cycle. After charging in the same way as the first cycle, discharge at a constant current at a current value of 20 m A until the circuit voltage reaches 2.5 V. At this time, the discharge capacity of the first cycle and the second cycle For the discharge capacity, evaluate the rapid discharge efficiency according to the following formula 30 312 / Invention Specification (Supplement) / 93-02 / 92136136 200414579. Rapid discharge efficiency (%) = (discharge capacity in the second cycle) (discharge capacity in the first cycle)
xlOO 又，此等評價試驗是另外以6 m A的電流值進行定電 電至電路電壓達到OmV為止。接著，在電路電壓達到 時，切換成定電壓充電，進而繼續充電至電流值為20 其後停止1 2 0分鐘。 接著以6mA的電流值進行定電流放電至電路電壓達 2 . 5 V為止。重複進行此充放電2 0循環，求得在第1 和第2 0循環之放電容量，由下式計算循環特性。 流充 OmV μ A， 到 循環 循環特性(％)= (第20循環的放電容量) (第1循環的放電容量）x100. In these evaluation tests, the electric power is fixed at a current value of 6 m A until the circuit voltage reaches 0 mV. Then, when the circuit voltage reaches, it switches to constant voltage charging, and then continues charging to a current value of 20 and then stops for 120 minutes. Then, perform a constant current discharge at a current value of 6 mA until the circuit voltage reaches 2.5 V. This 20 cycle of charge and discharge was repeated to obtain the discharge capacity at the 1st and 20th cycles, and the cycle characteristics were calculated by the following formula. Flow charge OmV μ A to cycle Cycle characteristic (%) = (discharge capacity at 20th cycle) (discharge capacity at 1st cycle)
xlOO 〈黑鉛〉 黑鉛是使用構成本發明的複合黑鉛粒子芯材，在以 實施例和比較例使用具有表1所示的物性之造粒化黑 該造粒化黑船是使用C 〇 u n t e r j e t m i 1 1 200AFG(Hosokawa micronC^S: )ϋ ) ^ 平均粒徑 30" m 片天然黑鉛，是經由以空氣壓力3 0 0 k P a、經由在機器 環1小時造粒而成的，去除所得到造粒化黑热中粒徑 5 " in以下之造粒化不充分的微粉，又，去除粗粉使大 7 5 μ ηι以下。 3丨2/發明說明書(補件)/93-02/92136136 下的 錯。 之鱗 内循 在 小在 31 200414579 表1 造粒化黑鉛 比表面 積 (m 2 / g ) 平均粒 徑 (β m) CxP- 見 兩 比 L c (nin ) La (n m ) d 〇 0 2 (nm ) R值 半值 幅度 3. 8 20 2.0 55 56 0.3356 0.08 25 (實施例1 ) 在乙二醇500g和六亞曱基四胺 (hexamethylenetetramine) 2. 5 g的混合物中添力口 S分搭樹 脂（殘碳4 0 % ) 2 5 g，在溶解後的溶液中，添加造粒化黑鉛（平 均粒徑2 0 // m·、寬高比2) 9 0 g，在分散狀態中攪拌。接著 在減壓下，以1 5 0 °C蒸餾去除溶劑，得到有樹脂被覆之造 粒化黑鉛，花5小時在空氣中將此樹脂被覆黑鉛粒子升溫 至2 7 0 °C為止，進而在2 7 0 °C保持2小時使樹脂被覆材固 化。將此固化物粉碎至大小在可過篩7 5 // m以下，接著在 氮氣環境下，以1 0 0 0 °C進行前碳化處理，進而以3 0 0 0 °C 進行碳化得到有1 0 %被覆量之本發明的複合黑鉛粒子。 又，為了估計實施例1碳化物層之結晶性，調製實施例 1的被覆材中沒有添加造粒化黑鉛、賦與實施例1相同累 積熱（h e a t h i s t 〇 r y )之被覆材碳化物，以X線繞射測定，d (1 〇 2為0 . 3 3 6 6 n m、L c 3 8 η m，可以確認結晶性比作為芯材之造 粒化黑雜之d u。2、L c (表1 ) 低一些。 (實施例2 ) 在苯S分39g和37%甲酸水（formalin)66g和六亞甲基四 月安（h e X a m e t h y 1 e n e t e t r a ni i n e ) 4 g所構成白勺溶液中添力口造 32 312/發明說明書(補件)/93-02/92136】36 200414579 粒化黑鉛（平均粒徑2 0 // m、寬高比2 ) 1 1 0 g，在分散狀態 中攪拌，在9 (TC加熱使單體聚合、使酚醛樹脂被覆在造粒 化黑鉛上，過濾取出樹脂被覆黑鉛粒子。此被覆黑鉛粒子 具有樹脂分2 0 %、換算殘碳為1 0 % )之被覆層。花5小時在 空氣中將此被覆黑鉛粒子升溫至2 7 0 °C為止，進而在2 7 0 °C保持2小時使被覆材固化。將此固化物粉碎至大小在可 過筛7 5 //丨η以下，接著在氮氣環境下，以1 0 0 0 °C進行前碳 化處理，進而以3 0 0 0 °C進行碳化得到有1 0 %被覆量之本發 明的複合黑鉛粒子。 (實施例3 ) 在煤焦輕油（tar light oil)500g和六亞曱基四胺 (hexamethylenetetramine) 1 . 5 g白勺混合物中添力口煤系瀝 青（軟化點1 0 5 °C 、殘碳6 0 % ) 6 · 7 g和S分酿樹脂（殘碳 4 0 % ) 1 5 g之溶液中，添加造粒化黑鉛（平均粒徑2 0 // m、寬 高比2 ) 9 0 g，在分散狀態中攪拌。接著在減壓下，以1 5 0 °C蒸餾去除溶劑中的煤焦輕油，得到有瀝青/樹脂混合被 覆黑鉛，花5小時在空氣中將此被覆黑鉛粒子升溫至2 7 0 °C為止，進而在2 7 0 °C保持2小時使被覆材固化。將此固 化物粉碎至大小在可過篩7 5 // m以下，接著在氮氣環境 下，以1 0 0 0 °C進行前碳化處理，進而以3 0 0 (TC進行碳化 得到有1 0 %被覆量之本發明的複合黑鉛粒子。 (實施例4 ) 在混合苯酚2 0 g和3 7 %曱醛水3 3 g和六亞曱基四胺 (li e X a ni e t h y 1 e n e t e t r a ni i n e ) 2 g和煤系中間相瀝青微粉（平 33 3 12/發明說明書(補件)/93-02/92136136 200414579 均粒徑4 // m、軟化點3 5 0 °C 、殘碳8 0 % ) 7 . 5 g所構成的溶 液中添力口造粒化黑毅（平均粒徑2 0 // m、寬高比2 ) 1 1 0 g， 在分散狀態中攪拌。以9 0 °C使上述成分進行聚合、被覆在 造粒化黑鉛上。接著，過濾取出樹脂被覆黑鉛粒子，此造 粒化黑絡為遞青複合樹脂所被覆（瀝青複合樹脂分1 8 %、換 算殘碳為1 0 %)。花5小時在空氣中將此樹脂被覆黑鉛粒子 升溫至2 7 0 °C為止，進而在2 7 0 °C保持2小時使被覆材固 化。將此固化物粉碎至大小在可過篩7 5 // m以下，接著在 氮氣環境下，以1 0 0 0 °C進行前碳化處理，進而以3 0 0 0 °C 進行碳化得到有1 0 %被覆量之本發明的複合黑鉛粒子。 (比較例1 ) 在乙二醇500g和六亞曱基四胺 (hexamethylenetetramine) 0 . 1 g的混合物中添力口酉分酸植] 脂（殘碳4 0 % ) 1 g，在溶解後的溶液中，添加造粒化黑鉛（平 均粒徑2 0 // m、寬高比2 ) 1 0 0 g，在分散狀態中攪拌。接著 在減壓下，以1 5 0 °C蒸餾去除溶劑，得到樹脂被覆黑鉛粒 子，花5小時在空氣中將此被覆黑鉛粒子升溫至2 7 0 °C為 止，進而在2 7 0 °C保持2小時使樹脂被覆材固化。將此固 化物粉碎至大小在可過篩7 5 // m以下，接著在氮氣環境 下，以1 0 0 0 °C進行前碳化處理，進而以3 0 0 0 °C進行碳化得 到有0 . 4 %被覆量之比較例的複合黑热粒子。 (比較例2 ) 在煤焦輕油（t a r 1 i g h t〇i 1 ) 5 0 0 g和六亞曱基四胺 (hexamethylenetetramine) 6 g白勺混合物所構成白勺溶液中 34 3丨2/發明說明書(補件)/93-02/92136136 200414579 添加酚醛樹脂（殘碳4 Q % ) 6 Q g，添加造粒化黑鉛（平均粒徑 2 0 v m、寬高比2 ) 7 6 g，在分散狀態中攪拌。接著在減壓 下，以1 5 (TC蒸餾去除溶劑，得到樹脂被覆黑鉛粒子，花 5小時在空氣中將此被覆黑鉛粒子升溫至2 7 0 °C為止，進 而在2 7 0 °C保持2小時使樹脂被覆層固化。將此固化物粉 碎至大小在可過篩7 5 " πι以下，接著在氮氣環境下，以1 0 0 0 °C進行前碳化處理，進而以3 0 0 0 °C進行碳化得到有2 4 %被 覆量之比較例的複合黑錯粒子。 (比較例3 ) 在混合S分酸樹脂（殘碳4 0 % ) 0 . 6 g和煤系遞青（軟化點1 0 5 °C 、殘碳6 0 % ) 0 . 4和煤焦輕油5 0 0 g和六亞曱基四胺 (hexamethylenetetramine) 0· lg戶斤構成白勺溶液中添力口造 粒化黑鉛（平均粒徑2 0 // m、寬高比2 ) 1 0 0 g，在分散狀態 中攪拌。接著在減壓下，以1 5 0 °C蒸餾去除煤焦輕油，得 到被覆黑鉛粒子，花5小時在空氣中將此樹脂被覆黑鉛粒 子升溫至2 7 0 °C為止，進而在2 7 0 °C保持2小時使被覆材 固化。將此固化物粉碎至大小在可過篩7 5 // m以下，接著 在氮氣環境下，以1 0 0 0 °C進行前碳化處理，進而以3 0 0 0 °C進行碳化得到有0 . 4 8 %被覆量之比較例的複合黑鉛粒 子。 (比較例4 ) 在由紛酸樹脂（殘碳4 0 % ) 3 0 g和煤系瀝青（軟化點1 0 5 °C 、殘碳6 0 % ) 2 0 g和煤焦輕油5 0 0 g和六亞甲基四胺 (hexamethylenetetramine) 6 g所構成白勺溶液中添力口造粒 35 3 12/發明說明書(補件)/93-02/92136136 200414579 化黑鉛（平均粒徑2 0 μ ηι、寬高t匕2 ) 7 6 g，在 拌。接著在減壓下，以1 5 0 °C蒸餾去除煤焦4 脂被覆黑鉛粒子，花5小時在空氣中將此樹 子升溫至2 7 Ot：為止，進而在2 7 0 °C保持2 /J 固化。將此固化物粉碎至大小在可過篩7 5 // 在氮氣環境下，以1 0 0 0 °C進行前碳化處理， t進行碳化得到有2 4 %被覆量之比較例的複1 (比較例5 ) 在實施例1中，除了不進行任何被覆處理 施例1相同所得到之造粒化黑鉛。 (比較例6 ) 在煤焦輕油5 0 0 g中溶解煤系瀝青（軟化點 6 0 % ) 1 6 . 7 g，添加造粒化黑鉛（平均粒徑2 0 , 2 ) 9 0 g，在分散狀態中攪拌。接著在減壓下 餾去除溶劑中的煤焦輕油，得到有瀝青被覆 環境下將此被覆黑鉛粒子以1 0 0 0 °C進行前碳 至大小在可過篩7 5 // m以下。進而以3 0 0 0 °C 有1 0 %被覆量之以往技術的複合黑鉛粒子。 (比較例7 ) 在比較例6中，除了未進行3 0 0 0 °C碳化外 例6相同所得到相當於以往技術的複合黑鉛 C比較例8 )xlOO <Black lead> Black lead is a composite black lead particle core material constituting the present invention. In the examples and comparative examples, granulated black having physical properties shown in Table 1 is used. The granulated black ship uses C. unterjetmi 1 1 200AFG (Hosokawa micronC ^ S:) ϋ) ^ average particle size of 30 " m pieces of natural black lead are obtained by granulating in a machine ring for 1 hour at an air pressure of 300 kPa and removing The obtained granulated black heat medium particle size of 5 " in or less was insufficiently granulated fine powder, and the coarse powder was removed to make it larger than 7 5 μηι. 3 丨 2 / Invention Specification (Supplement) / 93-02 / 92136136 The internal scale of the scale is small at 31 200414579 Table 1. Specific surface area of granulated black lead (m 2 / g) Average particle size (β m) CxP- See two ratios L c (nin) La (nm) d 〇0 2 ( nm) R value half-value amplitude 3. 8 20 2.0 55 56 0.3356 0.08 25 (Example 1) Add a mixture of 500 g of ethylene glycol and hexamethylenetetramine 2.5 g to add S Resin (residual carbon 40%) 2 5 g, in the dissolved solution, add granulated black lead (average particle size 2 0 // m ·, aspect ratio 2) 9 0 g, and stir in a dispersed state . Then, under reduced pressure, the solvent was distilled off at 150 ° C to obtain granulated black lead coated with a resin. The resin-coated black lead particles were heated to 27 ° C in air for 5 hours, and further The resin coating material was cured by holding it at 2 70 ° C for 2 hours. The solidified product is crushed to a size that can be sieved below 7 5 // m, and then pre-carbonized at 100 ° C under a nitrogen atmosphere, and then carbonized at 3 0 0 ° C to obtain 10 % Coating amount of the composite black lead particles of the present invention. In addition, in order to estimate the crystallinity of the carbide layer of Example 1, the coating material of the coating material of Example 1 was prepared without adding granulated black lead, and the coating material of the same accumulated heat (heathistory) as that of Example 1 was prepared. X-ray diffraction measurement, d (10 2 is 0.336 nm, L c 3 8 η m, it can be confirmed that the crystallinity is higher than that of the granulated black impurity du as the core material. 2, L c (Table 1) Lower. (Example 2) Add 39 g of benzene S, 66 g of 37% formic acid (formalin) and 4 g of hex amethy 1 enetetra ni ine. Likouzao 32 312 / Invention Specification (Supplement) / 93-02 / 92136] 36 200414579 Granulated black lead (average particle size 2 0 // m, aspect ratio 2) 1 1 0 g, stirred in a dispersed state At 9 ° C, the monomers are polymerized, the phenolic resin is coated on the granulated black lead, and the resin-coated black lead particles are filtered out. The coated black lead particles have a resin content of 20% and a residual carbon equivalent of 10%. ). The coated black lead particles are heated to 27 ° C in the air for 5 hours, and then kept at 2700 ° C for 2 hours to fix the coating. This solidified product is pulverized to a size that can be sieved below 7 5 // 丨 η, and then subjected to pre-carbonization treatment at 100 ° C in a nitrogen atmosphere, and then carbonized at 3 0 0 ° C to obtain The composite black lead particles of the present invention have a coating amount of 10%. (Example 3) Added to a mixture of 500 g of tar light oil and 1.5 g of hexamethylenetetramine To the solution of Likou coal-based asphalt (softening point 105 ° C, residual carbon 60%) 6 · 7 g and S fractionation resin (residual carbon 40%) 15 g, granulated black lead ( The average particle diameter is 2 0 // m, and the aspect ratio is 2) 9 0 g, and the mixture is stirred in a dispersed state. Then, the coal tar light oil in the solvent is distilled off at 150 ° C under reduced pressure to obtain an asphalt / The resin was mixed with black lead, and the coated black lead particles were heated to 270 ° C in the air for 5 hours, and then kept at 270 ° C for 2 hours to cure the coating material. The cured product was pulverized to a size of It can be sieved below 7 5 // m, and then under carbon atmosphere at 100 ° C for pre-carbonization treatment, and then carbonized at 3 0 (TC to obtain a hair coating with 10% coverage (Example 4) In a mixture of 20 g of phenol and 3 3 g of aldehyde water 3 3 g and li e X a ni ethy 1 enetetra ni ine 2 g and coal Mesophase pitch powder (flat 33 3 12 / Invention Specification (Supplement) / 93-02 / 92136136 200414579 Average particle size 4 // m, softening point 3 50 ° C, residual carbon 80%) 7.5 g The resulting solution was granulated with black powder (average particle diameter 2 0 // m, aspect ratio 2) 1 1 0 g, and stirred in a dispersed state. The above components were polymerized at 90 ° C and covered with granulated black lead. Next, the resin-coated black lead particles were taken out by filtration, and the granulated black network was covered with a green composite resin (the asphalt composite resin was 18%, and the residual carbon was 10%). The resin-coated black lead particles were heated to 270 ° C in the air for 5 hours, and then maintained at 270 ° C for 2 hours to cure the coating material. The solidified product is crushed to a size that can be sieved below 7 5 // m, and then pre-carbonized at 100 ° C under a nitrogen atmosphere, and then carbonized at 3 0 0 ° C to obtain 10 % Coating amount of the composite black lead particles of the present invention. (Comparative Example 1) To a mixture of 500 g of ethylene glycol and 0.1 g of hexamethylenetetramine (0.1 g), 1 g of fat (40% carbon residue) was dissolved. Granulated black lead (average particle diameter 2 0 // m, aspect ratio 2) 100 g was added to the solution, and stirred in a dispersed state. Then, under reduced pressure, the solvent was distilled off at 150 ° C to obtain resin-coated black lead particles, and the coated black lead particles were heated in the air to 270 ° C for 5 hours, and then at 270 ° C. C was held for 2 hours to cure the resin coating material. This solidified product is crushed to a size that can be sieved below 7 5 // m, and then subjected to pre-carbonization treatment at 100 ° C in a nitrogen atmosphere, and then carbonized at 3 0 0 ° C to obtain 0. Composite black heat particles of a comparative example with a 4% coating amount. (Comparative Example 2) In a solution consisting of a mixture of coal tar light oil (tar 1 ight〇i 1) 500 g and hexamethylenetetramine 6 g 6 (Supplement) / 93-02 / 92136136 200414579 Add phenolic resin (residual carbon 4 Q%) 6 Q g, add granulated black lead (average particle size 20 vm, aspect ratio 2) 7 6 g, disperse Stir in the state. Then, under reduced pressure, the solvent was distilled off at 15 ° C. to obtain resin-coated black lead particles, and the coated black lead particles were heated in the air to 270 ° C for 5 hours, and then at 270 ° C. Hold for 2 hours to cure the resin coating layer. This cured product is pulverized to a size that can be sieved below 7 5 " π, and then subjected to pre-carbonization treatment at 100 ° C. in a nitrogen atmosphere, and further to 3 0 0 Carbonized at 0 ° C to obtain composite black particles of the comparative example with a coating amount of 24%. (Comparative Example 3) S-acid resin (residual carbon 40%) was mixed with 0.6 g of coal-based greening (softening) Point 1 0 5 ° C, residual carbon 60%) 0.4 and coal tar light oil 5 0 g and hexamethylenetetramine 0 · lg household weight to form a granule in the solution Black lead (average particle size 2 0 // m, aspect ratio 2) 1 0 0 g, stirred in a dispersed state. Then, under reduced pressure, the coal tar light oil was distilled off at 150 ° C to obtain a coating. Black lead particles. Take 5 hours to heat up this resin-coated black lead particles to 270 ° C in the air, and then hold them at 270 ° C for 2 hours to cure the coating material. This is cured The material is pulverized to a size that can be sieved below 7 5 // m, and then pre-carbonized at 100 ° C in a nitrogen atmosphere, and then carbonized at 3 0 0 ° C to obtain 0.48%. Composite black lead particles of a comparative example in the amount of coating. (Comparative Example 4) 30 g of phenolic resin (residual carbon 40%) and coal-based pitch (softening point 105 ° C, residual carbon 60%) 2 0 g and coal tar light oil 5 0 g and hexamethylenetetramine 6 g solution in a white spoon solution 35 3 12 / Invention specification (Supplement) / 93-02 / 92136136 200414579 chemical black lead (average particle size 20 μηι, width and height 2) 7 6 g, stirring. Then under reduced pressure, remove the coal char 4 fat-coated black lead particles at 150 ° C, Spend 5 hours in the air to heat up this tree to 2 7 Ot: and then solidify at 2 / J at 2 0 ° C. Crush this cured product to a size that can be sieved 7 5 // Under nitrogen environment, The pre-carbonization treatment was performed at 100 ° C, and the carbonization of t was performed to obtain a duplicate 1 of a comparative example having a coating amount of 24% (Comparative Example 5). In Example 1, the same procedure as in Example 1 was performed except that no coating treatment was performed. Get made (Comparative Example 6) Dissolve coal-based asphalt (softening point 60%) in coal tar light oil 500 g (1.6%), and add granulated black lead (average particle size 20, 2) ) 90 g, stirring in a dispersed state. Then, the coal tar light oil in the solvent is distilled off under reduced pressure, and the black lead particles coated with this bitumen are subjected to precarbon at 100 ° C to a size that can be sieved below 7 5 // m. Furthermore, it is a composite black lead particle of the prior art which has a coating amount of 10% at 300 ° C. (Comparative Example 7) In Comparative Example 6, except that carbonization was not carried out at 3 0 0 ° C, the same composite black lead as in the prior art obtained in Example 6 was obtained. Comparative Example 8)
在實施例1中，除了使用在保持鱗片狀下 而成之物（平均粒徑1 5 // m、寬高比3 . 5 )作I 3丨2/發明說明書(補件)/93-02/92136136 分散狀態中攪 瘦油，得到樹 脂被覆黑鉛粒 、時使被覆材 m以下，接著 進而以3 0 0 0 ^黑鉛粒子。 外，其他與實 1 0 5 °C 、殘碳 111、寬高比 ，以150°C蒸 黑鉛，在氮氣 化處理，粉碎 進行碳化得到 ，其他與比較 粒子。 施行去角處理 b黑鉛粒子（雖 36 200414579 然對鱗片狀之天然黑鉛賦與機械外力，但是未達到球另 以外，其他與實施例1相同所得到相當於以往技術的 黑鉛粒子。 在表2 - 1和表2 - 2顯示實施例及比較例的複合黑鉛 之粉體特性。 在本發明之實施例1〜4中，造粒化黑鉛為擬定好適 值之碳化材料所被覆。和沒有碳化材料的比較例5比 得知雖然放電容量稍微降低，但是可以維持高放電容 初期充放電效率、急速放電效率、及循環特性亦優良 別是，作為熱固化性樹脂類，使用酚醛樹脂的單體含 當作原料之實施例2、4，具有優良的急速放電效率和 特性。 另一方面，在沒有碳化材料之比較例5和碳化材料 粒化黑鉛的被覆不充分之比較例1、3，初期充放電教 急速放電效率及循環特性顯著降低。相反地，在碳化 比合適範圍更多的比較例2、4，由於被覆時熔融黏著 合黑鉛粒子粉碎，碳化材料剝落，對初期充放電效率 改善效果不佳，又，放電容量顯著降低。比表面積增 由碳化材料的剝離而得到確認。 碳化材料中沒有使用熱固化性樹脂之相當於以往技 之比較例6的情況，碳化材料的結晶性太高、R值降 初期充放電效率降低。此外，碳化溫度從3 0 0 0 °C ，低 為1 0 0 0 °C之比較例7的情況，除了放電容量顯著降伯 急速放電效率和循環特性亦變差。又，粒狀黑鉛之寬 312/發明說明書(補件)/93-02/92136136 己化） 複合 粒子 度R 較， 量、 。特 有體 循環 對造 率、 材料 之複 等之 力口可 術 低、 溫化 外， 南比 37 200414579 不符合本發明規定之相當於以往技術之比較例8的情況， 由於複合黑鉛粒子的鱗片形狀其急速放電效率和循環特性 亦變差。In Example 1, except that the product (average particle size 1 5 // m, aspect ratio 3.5) was used while maintaining the scaly shape as I 3 丨 2 / Invention Specification (Supplement) / 93-02 / 92136136 Stir the thin oil in a dispersed state to obtain resin-coated black lead particles, so that the coating material is made m or less, and then use 3 0 0 ^ black lead particles. In addition, the others are compared with solids at 105 ° C, residual carbon 111, and aspect ratio. The black lead is steamed at 150 ° C, nitrogenized, pulverized, and carbonized to obtain. Others are compared with particles. Debuffing black lead particles (Although 36 200414579 imparts mechanical external force to the scale-like natural black lead, but does not reach the sphere, other black lead particles are obtained in the same manner as in Example 1 except for the conventional technology. Table 2-1 and Table 2-2 show the powder characteristics of the composite black lead of Examples and Comparative Examples. In Examples 1 to 4 of the present invention, the granulated black lead is covered with a carbonized material of a predetermined suitable value. Compared with Comparative Example 5 without a carbonized material, it is found that although the discharge capacity is slightly reduced, the initial charge and discharge efficiency, rapid discharge efficiency, and cycle characteristics of the high discharge capacity can be maintained. In addition, as the thermosetting resin, a phenol resin is used. The monomers of Examples 2 and 4 have excellent rapid discharge efficiency and characteristics. On the other hand, Comparative Example 5 without the carbonized material and Comparative Example 1 with insufficient coating of the granulated black lead of the carbonized material , 3, the initial charge and discharge teaches rapid discharge efficiency and cycle characteristics are significantly reduced. In contrast, in Comparative Examples 2 and 4, which had more carbonization than the appropriate range, black lead was melted and adhered during coating. Pulverization of particles, peeling of carbonized materials, poor initial charge and discharge efficiency improvement, and significant reduction in discharge capacity. Increase in specific surface area was confirmed by the peeling of carbonized materials. The equivalent of conventional technology without the use of thermosetting resins in carbonized materials In the case of Comparative Example 6, the crystallinity of the carbonized material was too high, and the charge and discharge efficiency decreased in the initial stage when the R value decreased. In addition, the case of Comparative Example 7 where the carbonization temperature was as low as 300 ° C and as low as 100 ° C In addition to the significant reduction in discharge capacity, the rapid discharge efficiency and cycle characteristics also deteriorate. Also, the width of granular black lead 312 / Invention Specification (Supplement) / 93-02 / 92136136 has been made) The composite particle size R is smaller than the amount, . The power of the unique systemic circulation to the production rate, the recovery of materials, etc. is low, and the temperature is outside, and Nanbei 37 200414579 does not meet the requirements of the present invention and is equivalent to the comparative example 8 of the prior art. Due to the scale shape of the composite black lead particles Its rapid discharge efficiency and cycle characteristics also deteriorate.
312/發明說明書(補件)/93-02/92136136 38 200414579 72嵴 複合黑鉛粒子之寬高比 CD CD οα CD οα CD οά ◦ οα ◦ CO οά CD (>0 τ—Η c^i οα οά LO CO 碳材d〇02/ 黑船d〇02 1. 0030 1. 0027 1. 0020 1. 0023 1. 0030 1. 0030 1. 0020 1. 0020 1 1.0009 1.0286 1.0030 拉曼分之光 R值 cn> τ < CD 〇〇 τ—Η C3> 1 aai τ—Η CD CO τ i <ZD CD CD 卜 CO 〇 CD r—Η ο 〇〇 οα CD 0. 08 ο- CD 〇〇 寸 CD LO CN1 CD 比表面積 (m2/g) τ··Η Η c^> ο ν_·Η 1丨丨― CO y ''< τ—Η c<i CO 卜 CO* 1 · CO 〇〇 CO 寸 1 i ， 1 CO CN1 最後碳化溫度 (°C) 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 ! _1 1000 3000 碳材之比率 (%) CD CD 10(Α:Β-6:4) 10(A:B=5:5) ο 寸 ο 寸 (ΝΙ 0.48(A:B-6:4) 24(A:B-6:4) CD ο CD cr> 石炭材之原料 酚醛樹脂 !苯酚單體 β分酸樹脂（A) +煤系 1 遞青（B ) 苯酚單體（A) +煤系 中間相遞青（B) 酚醛樹脂 酚醛樹脂 酚醛樹脂（A) +煤系 遞青（B) 酚醛樹脂（A) +煤系 瀝青（B) 1 煤系瀝青 煤系瀝青 酚醛樹脂 試料 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 t匕車交彳列4 比較例5 比較例6 比較例7 比較例8312 / Invention (Supplement) / 93-02 / 92136136 38 200414579 72 嵴 Aspect ratio of composite black lead particles CD CD οα CD οα CD οά ◦ οα ◦ CO οά CD (> 0 τ—Η c ^ i οα οά LO CO Carbon material 〇02 / Black ship 〇02 1. 0030 1. 0027 1. 0020 1. 0023 1. 0030 1. 0030 1. 0020 1. 0020 1 1.0009 1.0286 1.0030 Raman light R value cn > τ < CD 〇〇τ—Η C3> 1 aai τ—Η CD CO τ i < ZD CD CD CO CO 〇CD r—Η ο 〇〇οα CD 0. 08 ο- CD 〇〇inch CD LO CN1 CD specific surface area (m2 / g) τ ·· Η Η c ^ > ο ν_ · Η 1 丨 丨 CO y '' < τ—Η c < i CO COCO * 1 · CO 〇〇CO inch 1 i , 1 CO CN1 Final carbonization temperature (° C) 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000 3000! _1 1000 3000 Carbon material ratio (%) CD CD 10 (Α: Β-6: 4) 10 (A: B = 5: 5) ο inch ο inch (ΝΙ 0.48 (A: B-6: 4) 24 (A: B-6: 4) CD ο CD cr > Phenolic resin, the raw material for carbon materials! Phenol monomer β-acid resin ( A) + Coal series 1 Dicyanide (B) phenol monomer (A) + Coal series mesophase dicyanide (B) Phenolic resin Phenolic resin Phenolic resin (A) + Coal-based diazo (B) phenolic resin (A) + coal-based pitch (B) 1 Coal-based pitch Coal-based pitch phenolic resin sample Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 t dagger cross train 4 comparative example 5 comparative example 6 comparative example 7 comparative example 8
6rn9Γη19ΓηlfN6/s-e6/ff}ffi)*^;^s餾/(Νί e 200414579 表2 - 2 試料 放電容量 (mAh/g) 初期充放電效率 (%) 急速放電效率 (%) 循環特性 (%) 實施例1 363 95 91 92 實施例2 365 95 93 94 實施例3 360 94 94 95 實施例4 362 94 95 95 比較例1 371 90 74 84 比較例2 344 91 81 88 比較例3 371 90 75 85 比較例4 342 91 85 89 比較例5 370 87 71 82 比較例6 366 88 90 91 比較例7 347 92 87 88 比較例8 363 91 69 78 312/發明說明書(補件)/93-〇2/92136136 200414579 (產業上之可利用性） 依照本發明，可以提供生產率高且低成本、作為鋰離子 二次電池的負極材料之合適複合黑鉛粒子。使用此複合黑 鉛粒子作為鋰離子二次電池的負極材料時，不僅可以達成 以往因兩難而難以達成之性能、亦即高的初期充放電效率 和大的放電容量等兩項性能，而且兼備優良的急速放電特 性和循環特性，因而使用本發明的複合黑鉛粒子，可以滿 足近年對電池高能量密度化之要求。此外，裝載本發明的 負極材料及鋰二次電池之機器，小型化及高性能化成為可 能，能夠廣泛地對產業有所頁獻。 【圖式簡單說明】 圖1為顯示充放電試驗用之鈕釦型評價電池構造之橫剖 面圖。 (元件符號說明） 1 外裝杯 2 負極（作用電極） 3 外裝罐 4 正極 5 隔離板 6 絕緣墊片 7 a 正極集電體 7 b 負極集電體 41 312/發明說明書(補件)/93-02/921361366rn9Γη19ΓηlfN6 / s-e6 / ff) ffi) * ^; ^ sstill / (Νί e 200414579) Table 2-2 Sample discharge capacity (mAh / g) Initial charge and discharge efficiency (%) Rapid discharge efficiency (%) Cycle characteristics (% ) Example 1 363 95 91 92 Example 2 365 95 93 94 Example 3 360 94 94 95 Example 4 362 94 95 95 Comparative Example 1 371 90 74 84 Comparative Example 2 344 91 81 88 Comparative Example 3 371 90 75 85 Comparative Example 4 342 91 85 89 Comparative Example 5 370 87 71 82 Comparative Example 6 366 88 90 91 Comparative Example 7 347 92 87 88 Comparative Example 8 363 91 69 78 312 / Invention Specification (Supplement) / 93-〇2 / 92136136 200414579 (Industrial availability) According to the present invention, it is possible to provide a suitable composite black lead particle having high productivity and low cost as a negative electrode material for a lithium ion secondary battery. Use this composite black lead particle as a lithium ion secondary battery In the case of a negative electrode material, not only the performance previously difficult to achieve due to the dilemma, that is, the two characteristics of high initial charge and discharge efficiency and large discharge capacity, but also excellent rapid discharge characteristics and cycle characteristics are achieved. Composite black lead particles can be full In recent years, there has been a demand for high energy density of batteries. In addition, a device equipped with the negative electrode material of the present invention and a lithium secondary battery can be miniaturized and high-performance, and can widely contribute to the industry. [Schematic explanation Figure 1 is a cross-sectional view showing the structure of a button-type evaluation battery for a charge-discharge test. (Element symbol description) 1 Outer cup 2 Negative electrode (active electrode) 3 Outer can 4 Positive electrode 5 Separator plate 6 Insulating gasket 7 a Positive current collector 7 b Negative current collector 41 312 / Invention Manual (Supplement) / 93-02 / 92136136