201115814 \ 六、發明說明： 【發明所屬之技術領域】 本發明係關於鋰蓄電池用負極活性物質，鋰蓄電池用 負極電極，使用此等之車載用鋰蓄電池，及鋰蓄電池用負 極活性物質之製造方法。 【先前技術】 鋰蓄電池，與其他蓄電池相比具有高能量密度，所以 可達到小型化·輕量化，所以廣泛地運用在行動電話、個 人電腦、可攜式資訊終端（PDA : Personal Digital Assistant (個人數位助理））及手持式攝影機等之可攜式 電子機器的電源，今後亦可預見到其需求日益提高。 此外’爲了對應能源問題或環境問題，係已開發出電 動車以及組合有鎳氫電池驅動的馬達與汽油引擎之油電混 合車（HEV: Hybrid Electric Vehicle)，其普及台數正增 加中。此等汽車中，係要求所用之電池的更高性能化，作 爲因應此要求者，鋰蓄電池乃受到矚目。 鋰蓄電池中，負極材料（負極活性物質）一般係使用 安全性及壽命方面較佳之碳材料。碳材料中，石墨材料係 在至少2,000 °C以上，一般爲2,6〇0〜3,000 °C的高溫下所得 之具有高能量密度之較佳材料，但在高輸出入特性及循環 特性方面仍存在著課題。因此，例如在電力儲存用或電動 車等之高輸出入用途中，主要係針對在較石墨材料更低之 溫度下進行燒結，其石墨化程度較低之低結晶碳材料的運 -5- 201115814 用進行硏究。 近年來’就油電混合車的更高性能化之觀點來看，對 於鋰蓄電池亦要求更高性能化，使其性能的提升成爲當務 之急。尤其作爲鋰蓄電池的特性，係要求可充分降低負極 側的電位來提升實質電池電壓，而顯現出充分高的輸出特 性者。 此外，係以能夠充分地供應作爲油電混合車的能量來 源之電流之方式，將鋰蓄電池的放電容量列舉爲重要特性 。除此之外，並以與充電電流量相比可充分地提高放電電 流量之方式，要求充電容量相對於放電容量之比率，亦即 初期效率可達較高者。 再者’爲了可在短時間內充電，鋰蓄電池較佳爲至高 電流密度爲止均可維持高充電容量，亦即要求容量維持率 可達較高者。亦即，係要求可在均衡性良好下提高此般輸 出特性、放電容量、初期效率、容量維持率等之特性❶ 以此般鋰蓄電池爲目的，係探討許多以焦炭或石墨等 之碳材料作爲負極材料者，然而，雖然可增大上述放電容 量，但其初期效率仍不足。此外，實質電池電壓不足，且 無法滿足近年來所要求的高輸出特性，亦無法滿足容量維 持率之要件。 例如在專利文獻1中，係揭示一種藉由有機化合物的 熱分解或燒結碳化所得之限定其特定的比表面積及X射線 繞射結晶厚度等之碳質材料，作爲運用插層或摻雜之負極 材料者，但在HEV用等之車載用途中，其性能仍不足。 201115814 專利文獻2中，係揭示一種將特定的被覆層設置於具 有類石墨構造之碳質等並進行熱處理所得之碳質材料，用 作爲負極材料者’專利文獻3中’係揭示一種將以在低溫 下經熱處理之焦炭爲原料，並且在非活性氣體環境下進行 熱處理來更進一步地去除雜質而具有相對較高的放電容量 之碳材料’作爲負極材料者，然而，兩者在HEV用等之車 載用途中’均非具有充分的電池特性者。 此外’專利文獻4中，係揭示一種以在500〜85〇t下將 石油或煤的生焦炭進行熱處理之經熱處理的生焦炭作爲負 極材料，藉此可供應充.放電容量大之鋰蓄電池者，但在 HEV用等之車載用途中，其輸出特性方面仍不足。 將以上述焦炭等作爲原料之低結晶碳材料用作爲鋰蓄 電池用負極材料之硏究，大部分均用以改善作爲小型可攜 式機器用電源之蓄電池用負極材料的特性，關於具有適合 於以HEV用蓄電池爲代表之大電流輸出入鋰蓄電池用的充 分特性之負極材料，目前仍處於未被開發出之情況。 另一方面，亦有探討將各種化合物添加於有機材料或 碳質材料以提升電池特性者。例如在專利文獻5中，係揭 示一種藉由將磷化合物添加於有機材料或碳質材料並進行 碳化所得之負極材料，專利文獻6中，係揭示一種將含有 硼及矽之碳材料進行石墨化所得之負極材料，然而，與上 述相同，兩者在HEV用等之車載用途中，其輸出特性等方 面仍未達實用化。 〔先前技術文獻〕 201115814 〔專利文獻〕 〔專利文獻1〕日本特開昭62_90863號公報 〔專利文獻2〕日本特開平6_5287號公報 〔專利文獻3〕日本特開平8_1〇2324號公報 〔專利文獻4〕日本特開平9_320602號公報 〔專利文獻5〕日本特開平3-137010號公報 〔專利文獻6〕日本特開平n-40 1 58號公報 【發明內容】 (發明所欲解決之課題） 本發明之課題，係以製得可充分地提升鋰蓄電池的輸 出特性，具備包含放電容量、初期效率及容量維持率之 HE V用等的車載用途所要求之實用特性之新穎的負極活性 物質者爲目的。 (用以解決課題之手段） 本發明者們係爲了達成上述目的而進行精心探討。結 果係發現到一種將相對於煤系及/或石油系（以下稱爲煤 系等）生焦炭100重量份而言，以經磷及硼換算分別爲0.1 重量份~6.0重量份的比率添加磷化合物及硼化合物之焦炭 材料進行燒結而成者爲特徵之鋰蓄電池用負極活性物質， 係可充分地降低鋰蓄電池的負極電位而提升實質電池電壓 ，並且具備輸出特性、放電容量、初期效率及容量維持率 等之車載用途所要求的實用特性，因而完成本發明。[Technical Field] The present invention relates to a negative electrode active material for a lithium secondary battery, a negative electrode for a lithium secondary battery, a lithium battery for use in the vehicle, and a method for producing a negative electrode active material for a lithium secondary battery . [Prior Art] Lithium batteries have high energy density compared with other batteries, so they can be reduced in size and weight, so they are widely used in mobile phones, personal computers, and portable information terminals (PDA: Personal Digital Assistant (personal). The power supply of portable electronic devices such as digital assistants) and hand-held cameras can be expected to increase in the future. In addition, in order to respond to energy problems or environmental problems, electric vehicles and hybrid electric vehicles (HEVs) equipped with nickel-hydrogen battery-powered motors and gasoline engines have been developed, and the number of popular vehicles is increasing. In these automobiles, the performance of the battery used is required to be higher. As a result of this requirement, the lithium secondary battery is attracting attention. In the lithium secondary battery, the negative electrode material (negative electrode active material) is generally a carbon material which is preferable in terms of safety and life. Among the carbon materials, the graphite material is a preferred material having a high energy density at a temperature of at least 2,000 ° C or higher, generally at a temperature of 2,6 〇 0 to 3,000 ° C, but still has high input and output characteristics and cycle characteristics. There are problems. Therefore, for example, in high-input applications such as power storage or electric vehicles, the main purpose is to perform sintering at a lower temperature than graphite materials, and the degree of graphitization is low. The low-crystalline carbon material is transported -5-201115814 Use it for research. In recent years, in view of the higher performance of hybrid electric vehicles, lithium batteries are also required to have higher performance, and the improvement of their performance has become a top priority. In particular, as a characteristic of a lithium secondary battery, it is required to sufficiently lower the potential on the negative electrode side to increase the substantial battery voltage, and to exhibit a sufficiently high output characteristic. Further, the discharge capacity of the lithium secondary battery is cited as an important characteristic in such a manner that the current of the energy source of the hybrid electric vehicle can be sufficiently supplied. In addition, the ratio of the charging capacity to the discharge capacity, that is, the initial efficiency can be higher, in such a manner that the discharge current can be sufficiently increased as compared with the amount of charging current. Further, in order to be able to be charged in a short time, it is preferable that the lithium secondary battery maintains a high charging capacity up to a high current density, that is, a capacity retention ratio is required to be higher. In other words, it is required to improve the characteristics of such output characteristics, discharge capacity, initial efficiency, capacity retention rate, etc. with good balance. For the purpose of lithium batteries, many carbon materials such as coke or graphite have been discussed. In the case of the negative electrode material, however, although the above discharge capacity can be increased, the initial efficiency is still insufficient. In addition, the actual battery voltage is insufficient, and the high output characteristics required in recent years cannot be satisfied, and the capacity maintenance rate cannot be satisfied. For example, in Patent Document 1, a carbonaceous material which is obtained by thermal decomposition or sintering carbonization of an organic compound to define its specific specific surface area and X-ray diffraction crystal thickness is used as a negative electrode using an intercalation or doping. Materials, but in the automotive applications such as HEV, the performance is still insufficient. 201115814 Patent Document 2 discloses a carbonaceous material obtained by providing a specific coating layer to a carbonaceous material having a graphite-like structure and heat-treating it, and as a negative electrode material, 'Patent Document 3' discloses that one will be The carbon material which has been subjected to heat treatment at a low temperature as a raw material and which is subjected to heat treatment in an inert gas atmosphere to further remove impurities and has a relatively high discharge capacity is used as a negative electrode material, however, both are used in HEV. In automotive applications, none of them have sufficient battery characteristics. Further, in Patent Document 4, a heat-treated raw coke which heat-treats petroleum or coal coke at 500 to 85 〇t is used as a negative electrode material, whereby a lithium battery having a large discharge capacity can be supplied. However, in the automotive applications such as HEV, the output characteristics are still insufficient. A low-crystalline carbon material using the above-mentioned coke or the like as a raw material for a lithium battery is mainly used for improving the characteristics of a negative electrode material for a battery used as a power source for a small portable device, and is suitable for The negative electrode material of the sufficient characteristics for the high-current output of the lithium battery represented by the HEV battery is still undeveloped. On the other hand, there are also discussions on adding various compounds to organic materials or carbonaceous materials to improve battery characteristics. For example, Patent Document 5 discloses a negative electrode material obtained by adding a phosphorus compound to an organic material or a carbonaceous material and carbonizing it. In Patent Document 6, a carbon material containing boron and lanthanum is graphitized. In the same manner as described above, the obtained negative electrode material has not yet been put into practical use in terms of output characteristics such as HEV. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In order to obtain a novel negative electrode active material which has a practical characteristic required for in-vehicle use such as HE V, which has a discharge capacity, an initial efficiency, and a capacity retention rate, it is an object of the present invention. (Means for Solving the Problem) The present inventors conducted intensive discussions in order to achieve the above object. As a result, it has been found that phosphorus is added in a ratio of 0.1 parts by weight to 6.0 parts by weight in terms of phosphorus and boron, respectively, with respect to 100 parts by weight of coke for coal and/or petroleum (hereinafter referred to as coal). The negative electrode active material for a lithium secondary battery, which is characterized by sintering a coke material of a compound and a boron compound, can sufficiently reduce the negative electrode potential of the lithium secondary battery and increase the substantial battery voltage, and has output characteristics, discharge capacity, initial efficiency, and capacity. The present invention has been completed by maintaining practical characteristics required for in-vehicle use such as maintenance rate.
-8- 201115814 本發明中所謂“煤系等之生焦炭”，係意味著使用延遲 焦化裝置等之焦炭化設備，在最高到達溫度爲400。(： ~700 °C左右之溫度下，將石油系及/或煤系重油實施24小時左 右的熱分解·聚縮合反應所得者。 發明之效果： 根據本發明，係能夠提供一種可充分地提升鋰蓄電池 的輸出特性，具備包含放電容量、初期效率及容量維持率 之HEV用等的車載用途所要求之實用特性，且性能均衡性 佳之負極活性物質。 【實施方式】 以下係根據鋰蓄電池用負極活性物質之實施形態，來 詳細說明本發明。 本發明之鋰蓄電池用負極活性物質，首先例如使用延 遲焦化裝置等之焦炭化設備，在最高到達溫度400 °C〜700 °C的溫度下，將煤系等之重油進行24小時的熱分解·聚縮 合反應，藉此製得煤系等之生焦炭。然後將所得之煤系等 之生焦炭塊狀物粉碎成預定大小。粉碎可使用工業上所用 之粉碎機，具體而言，例如可列舉出原子化硏磨機、雷蒙 硏磨機 '葉輪式硏磨機、球磨機、切割硏磨機、噴磨機、 雜合機等，但並不限定於此》 在此所使用之煤系等之重油，可爲石油系重油或煤系 重油’惟煤系重油者，其係具有富含芳香族性，且會與鋰-8- 201115814 In the present invention, the term "green coke such as coal-based" means a coke-forming apparatus using a delayed coker or the like, and has a maximum temperature of 400. (: The oil-based and/or coal-based heavy oil is subjected to thermal decomposition/polycondensation reaction for about 24 hours at a temperature of about ~700 °C. Effect of the invention: According to the present invention, it is possible to provide a sufficient improvement The output characteristics of the lithium battery include a practical property required for in-vehicle use such as a discharge capacity, an initial efficiency, and a capacity retention rate, and a negative electrode active material having excellent performance balance. [Embodiment] The following is based on a negative electrode for a lithium secondary battery. The present invention will be described in detail with respect to the embodiment of the active material. The negative electrode active material for a lithium battery of the present invention is first used, for example, in a coke gasification apparatus such as a delayed coker, at a temperature of up to 400 ° C to 700 ° C. The heavy oil such as coal is subjected to a thermal decomposition/polycondensation reaction for 24 hours to obtain a raw coke such as a coal system, and then the raw coke mass of the obtained coal system or the like is pulverized into a predetermined size. Specific examples of the pulverizer used include an atomization honing machine, a Raymond honing machine, an impeller honing machine, and a ball mill. Cutting honing mill, jet mill, hybrid machine, etc., but not limited to this. The heavy oil such as coal used here may be petroleum heavy oil or coal heavy oil 'only coal heavy oil, its system Rich in aromatics and will be associated with lithium
S -9 - 201115814 產生不可逆反應之N、S等之異質元素的含量較少之優點， 並且其揮發份亦低，所以較佳係使用煤系重油。 粉碎後之煤系等之生焦炭粉及煤系等之燒結焦炭粉的 大小並無特別限定，以中位徑所求取之平均粒徑，尤佳爲 5〜1 5μιη ’此時’ BET比表面積尤佳爲5m2/g以下。當平均 粒徑低於5 μ m時，比表面積過度增加，所得之鋰蓄電池的 初期效率有降低之疑慮。另一方面，當平均粒徑超過15 μπι 時’鋰蓄電池的充放電特性有降低之疑慮。當BET比表面 積高於5m2/g時，如上述般，比表面積過度增加，鋰蓄電 池的初期效率有降低之疑慮。BET比表面積，就形成細微 孔之觀點來看，較佳爲2m2/g以上。 上述焦炭粉中，係添加磷化合物及硼化合物。添加方 式，係調配上述煤系等之生焦炭粉與下列所示之量的磷化 合物及硼化合物’並放入預定的模型內來進行（第1添加 法）。 磷化合物及硼化合物的添加，亦可在獲得煤系等之生 焦炭塊狀物的時點來進行’以取代在獲得煤系等之生焦炭 粉後來進行之方式（第2添加法）。此時，係將煤系等之 生焦炭塊狀物放入至粉碎機，並同時將上述磷化合物及硼 化合物放入至前述粉碎機來進行前述塊狀物的粉碎，藉此 可獲得由添加有前述磷化合物及前述硼化合物所構成之煤 系等之生焦炭粉。 因此’由於在煤系等之生焦炭塊狀物的粉碎時，可同 時添加磷化合物及硼化合物，所以可省略在燒結時另外添S -9 - 201115814 The advantage of the content of the heterogeneous element such as N, S, etc. which produces an irreversible reaction is small, and the volatile content thereof is also low, so it is preferred to use a coal-based heavy oil. The size of the raw coke powder such as the coal-based coke powder and the coal-based pulverized coke powder is not particularly limited, and the average particle diameter obtained by the median diameter is preferably 5 to 15 μm η 'this time BET ratio The surface area is particularly preferably 5 m 2 /g or less. When the average particle diameter is less than 5 μm, the specific surface area excessively increases, and the initial efficiency of the obtained lithium secondary battery is lowered. On the other hand, when the average particle diameter exceeds 15 μm, the charge and discharge characteristics of the lithium secondary battery are lowered. When the BET specific surface area is higher than 5 m2/g, as described above, the specific surface area excessively increases, and the initial efficiency of the lithium secondary battery is lowered. The BET specific surface area is preferably 2 m 2 /g or more from the viewpoint of forming fine pores. Among the above coke powders, a phosphorus compound and a boron compound are added. In the addition method, the raw coke powder of the above-mentioned coal system and the amount of the phosphorus compound and the boron compound shown below are placed in a predetermined mold (first addition method). The addition of the phosphorus compound and the boron compound may be carried out in the case where a coke bromide such as a coal system is obtained, instead of being obtained by obtaining a raw coke powder such as a coal system (second addition method). In this case, a raw coke mass such as a coal system is placed in a pulverizer, and the phosphorus compound and the boron compound are simultaneously placed in the pulverizer to pulverize the lumps, thereby obtaining addition. There is a raw coke powder such as a coal compound composed of the phosphorus compound and the boron compound. Therefore, since the phosphorus compound and the boron compound can be simultaneously added during the pulverization of the raw coke mass of the coal system or the like, it is possible to omit the additional addition at the time of sintering.
-10- 201115814 加磷化合物等之操作’而能夠簡化鋰蓄電池用負極活性物 質的製造步驟全體。 惟上述第1添加法及第2添加法，均僅因添加之具體手 法的不同而使鋰蓄電池用負極活性物質的製造步驟有所差 異’鋰蓄電池用負極活性物質本身之輸出特性或放電容量 、初期效率、容量維持率幾乎不變。 上述磷化合物的添加量’相對於煤系等之生焦炭1 〇 〇 重量份而言，較佳係經磷換算爲0.1〜6.0重量份，更佳爲 0.5 ~5.0重量份。當添加量未達下限時，添加磷化合物之效 果可能有無法充分獲得之疑慮，另一方面，當添加量超過 上限時’焦炭表面的低結晶化進彳T，輸出特性有降低之疑 慮。 此外，上述硼化合物的添加量，相對於煤系等之生焦 炭100重量份而言，較佳係經硼換算爲0.1〜6.0重量份，更 佳爲0.5〜5.0重量份。當添加量未達下限時，添加硼化合物 之效果可能有無法充分獲得之疑慮，另一方面，當添加量 超過上限時，會有過度促進焦炭的碳化，並殘存未反應的 硼之疑慮，而有使鋰蓄電池用負極活性物質之輸出特性或 放電容量、初期效率 '容量維持率劣化之疑慮。 上述磷化合物，就容易調製成水溶液且具高安全性等 之觀點來看，較佳爲磷酸類。磷酸類尤佳爲使用磷酸類（ 正磷酸），但並不限定於此，可從直鏈狀聚磷酸或環狀聚 磷酸，或是各種磷酸酯化合物等當中適當地選擇使用。此 等磷酸類可單獨使用其中任1種或是調配2種以上使用。 5 -11 - 201115814 此外，上述硼化合物較佳爲使用碳化硼（b4c)。此 係由於即使碳化硼於燒結中產生分解，其分解所得之成分 亦僅爲用以達成本發明之目的的硼以及負極活化物質的母 材之焦炭的構成元素之碳，而不包含其他成分，所以可抑 制該其他成分對負極活化物質所造成的不良影響之故。 對此焦炭進行燒結。此燒結溫度，可將其最高到達溫 度設爲800°c以上、1400°c以下。較佳爲900°c〜1200°c， 更佳爲900°C〜1 100°C之範圍。當燒結溫度超過此上限時， 過度促進焦炭材料的結晶成長，有使鋰蓄電池用負極活性 物質之輸出特性或放電容量、初期效率、容量維持率劣化 之疑慮，此外，就量產性之觀點來看亦不佳。另一方面， 當燒結溫度低於此下限時，不僅無法進行充分的結晶成長 ’並且在焦炭的碳化過程中，磷化合物及硼化合物的添加 效果不足’同樣的，有使鋰蓄電池用負極活性物質之輸出 特性或放電容量、初期效率、容量維持率劣化之疑慮。 此外，最高到達溫度下的保持時間並無特別限定，但 較佳爲30分鐘以上。此外，燒結環境氣體並無特別限定， 可爲氬氣或氮氣等之非活性氣體，或是如旋轉窯般之非密 閉狀態下之非氧化性氣體環境，或是Riedhammer爐般之密 閉狀態下之非氧化性氣體環境》 當使用此般本發明之負極活性物質來構成鋰蓄電池時 ，相對應的正極，可使用含鋰的過渡金屬氧化物LiM ( 1 ) x〇2(式中，X爲OSxSl之範圍的數値，式中，M(l)表 示過渡金屬，係由 Co、Ni、Mn、Ti、Cr、V、Fe、Zn、A1 201115814 、Sn、In的至少 1種所構成），LiM ( 1 ) yM ( 2 ) 2.y〇4 ( 式中，y爲OSySl之範圍的數値，式中，M(l) 、M(2 )表示過渡金屬，係由Co、Ni、Μη、Ti、Cr、V、Fe、Zn 、Al、Sn、In的至少1種所構成），過渡金屬硫族化合物 (Ti、S2、NbSe 等），釩氧化物（V205、V6013、V2〇4、 V306等）及鋰化合物，一般SMxMo6Ch6-y(式中，x爲0$ xS4，y爲OSySl之範圍的數値，式中，Μ表示以過渡金 屬爲首之金屬，Ch表示硫族金屬）所表示之謝弗雷爾相（ Chevrel Phase)化合物，或是活性碳、活性碳纖維等之正 極活性物質。 此外，塡滿上述正極與負極之間之電解質，可使用以 往所知之任一種，例如可列舉出，LiC104、LiBF4、LiPF6 、LiAsF6 ' LiB ( C6H5 ) 、LiCl、LiBr、Li3S03、Li ( CF3SO2 ) 2N ' Li ( CF3SO2 ) 3C、Li ( CF3CH2OSO2 ) 2N ' Li ( CF3CF2CH2OSO2 ) 2N、Li ( HCF2CF2CH2OSO2 ) 2N ' Li ( ( CF3 ) 2CHOSO2 ) 2N、LiB[C6H3(CF3) 2]4 等之 1 種 或2種以上之混合物。 此外，非水系電解質，例如可使用碳酸丙烯酯、碳酸 乙烯酯、碳酸丁烯酯、碳酸氯乙烯酯、碳酸二甲酯、碳酸 二乙酯、碳酸乙基甲酯、1，1-二甲氧基乙烷、1,2 -二甲氧 基乙烷、1,2-二乙氧基乙烷' 丁內酯、四氫呋喃、2-甲 基四氫呋喃、1，3-二氧戊環、4-甲基-1,3-二氧戊環、甲氧 苯、二乙基醚、環丁楓、甲基環丁颯、乙腈、氯腈、丙腈 、硼酸三甲酯、矽酸四甲酯 '硝化甲烷、二甲基甲醯胺、 -13- 201115814 N-甲基咯烷酮、乙酸乙酯、正甲酸三甲酯、硝化苯、氯化 苯甲醯、溴化苯甲醯、四氫噻吩、二甲基亞楓、3-甲基-2· 噁唑烷酮、乙二醇、亞硫酸、二甲基亞硫酸等之單獨溶劑 或2種以上的混合溶劑。 當使用上述負極活性物質來構成負極時，一般係將聚 偏二氟乙烯（PVDF )等之氟系樹脂粉末或聚醯亞胺（PI )系樹脂、苯乙烯丁二烯橡膠（SBR )、羧甲基纖維素（ CMC )等之水溶性黏結劑構成爲碳質黏合劑，並使用N-甲 基咯烷酮（NMP )、二甲基甲醯胺或水、醇等之溶劑混合 此黏合劑與上述負極活性物質並藉此製作漿液，然後塗佈 於集電體上並進行乾燥來進行。 〔實施例〕 以下係根據實施例更具體地說明本發明。惟本發明之 內容並不限定於此等實施例。 (實施例1 ) 使用從煤系重油中去除喹啉不溶份之精製瀝青，並藉 由延遲焦化法在500 °c的溫度下進行24小時的熱處理，得 到所製造出之塊狀焦炭（生焦炭），藉由噴磨機進行微粉 碎及粒化，而獲得平均粒徑9.9μιη的生焦炭粉。 相對於上述所得之生焦炭粉1 〇〇重量份，添加磷酸酯 (I·4質量％活性磷固形樹脂：三光公司製之商品名稱爲 HCA，化學名稱：9，10 -二氫-9-噁-10-磷菲-10-氧化物） 201115814 25·0重量份（經磷換算：3 5重量份），以及碳化硼I”重 量份（經硼換算：1 · 5重量份）。 接著將添加磷酸酯及碳化硼而成之上述焦炭材料，以 600°C /小時的速度從室溫開始升溫，到達9〇<rc後（最高到 達溫度），再保持2小時來進行碳化處理（燒結），而得 鋰蓄電池用負極活性物質。 然後添加5質量％之作爲黏合劑的聚偏二氟乙烯（ PVDF ’ Kureha公司製）於鋰蓄電池用負極活性物質中， 以N -甲基咯烷酮（NMP)作爲溶劑並進行捏合而調製出漿 液’將此均一地塗佈於厚度1 8 μιη的銅箔而得負極電極箔。 將此負極電極箔進行乾燥，並模壓成爲預定的電流密度而 製作出電極薄片，從該薄片中裁切出直徑15mm(D的圓形 ，藉此製作出負極電極。爲了評估此負極電極之單極下的 電極特性，係使用裁切爲15.5 mm(D的金屬鋰作爲對極。 此外，係使用以lmol/Ι的濃度將1^??6溶解於碳酸乙烯 酯與碳酸二乙酯的混合溶劑（以體積比1: 1混合）者作爲 電解液，並使用丙烯的多孔質膜作爲分隔器來製作出硬幣 單元，而製得鋰蓄電池。在25 °c的恆溫下，且在將端子電 壓的充電下限電壓設爲0V、放電的上限電壓設爲1.5V之電 壓範圍內，實施5mA/cm2的定電流放電’並調查此時的放 電特性。結果如第1表所示。 (實施例2〜3 ) 實施例1中，係將所添加之磷酸酯的量與碳化硼的量 -15- 201115814 ，從經磷換算爲3.5重量份、經硼換算爲1.5重I 爲經磷換算爲2.5重量份、經硼換算爲2.5重量份 )，以及經磷換算爲1 · 5重量份、經硼換算爲3 . 實施例3 )，除此之外，其他進行與實施例1相|1 得鋰蓄電池。此外，係與實施例1相同來調查方 結果如第1表所示。 (比較例1 ) 使用生焦炭粉100重量份的焦炭材料且不 及碳化硼，除此之外，其他進行與實施例1相 得鋰蓄電池。此外，係與實施例1相同來調查 結果如第1表所示。 (比較例2 ) 使用生焦炭粉100重量份的焦灰材料且僅名 算爲5.0重量份之磷酸酯，除此之外，其他進行 相同之操作而得鋰蓄電池。此外’係與實施例 査放電特性。結果如第1表所示。 (比較例3 ) 使用生焦炭粉100重量份的焦炭材料且僅袭 算爲5.0重量份之碳化硼，除此之外，其他進行 相同之操作而得鋰蓄電池。此外，係與實施例 查放電特性。結果如第1表所示。 t份，變更 (實施例2 5重量份（ 0之操作而 ί電特性。 加磷酸酯 之操作而 電特性。 $加經磷換 與實施例1 1相同來調 ^加經硼換 與實施例1 1相同來調 -16- 201115814 (實施例4〜6 ) 實施例中’係將焦炭材料的燒結溫度（最高到達 溫度）從90(TC變更爲l〇〇〇°C ’除此之外，其他分別進行與 實施例1〜3相同之操作而得鋰蓄電池。此外，係與實施例i 相同來調查放電特性。結果如第1表所示。 (比較例4〜6 ) 比較例1 ~3中’係將焦炭材料的燒結溫度（最高到達 溫度）從900C變更爲1000C，除此之外，其他分別進行跑 比較例1〜3相同之操作而得鋰蓄電池。此外，係與實施例i 相同來調查放電特性。結果如第1表所示。 (實施例7〜9 ) 實施例1〜3中’係將焦炭材料的燒結溫度（最高到達 溫度）從900°C變更爲ll〇〇°C ’除此之外，其他分別進行與 實施例1 ~ 3相同之操作而得鋰蓄電池。此外，係與實施例J 相同來調查放電特性。結果如第1表所示。 (比較例7〜9 ) 比較例1〜3中，係將焦炭材料的燒結溫度（最高到達 溫度）從900°C變更爲1100°C，除此之外，其他分別進行與 比較例1〜3相同之操作而得鋰蓄電池。此外，係與實施例1 相同來調查放電特性。結果如第1表所示。 -17- 201115814 (實施例10〜12 ) 實施例1〜3中，係將焦炭材料的燒結溫度（最高到達 溫度）從90〇°C變更爲1 200。(：，除此之外，其他分別進行與 實施例1 ~3相同之操作而得鋰蓄電池。此外，係與實施例1 相同來調査放電特性。結果如第1表所示》 (比較例10~12 ) 比較例1〜3中，係將焦炭材料的燒結溫度（最高到達 溫度）從900°C變更爲1 200°C，除此之外，其他分別進行與 比較例1〜3相同之操作而得鋰蓄電池。此外，係與實施例1 相同來調查放電特性。結果如第1表所示。 (實施例13〜20 ) 實施例5中，係將所添加之磷酸酯的量與碳化硼的量 ’從經磷換算及經硼換算各爲2 · 5重量份，變更爲經磷換 算爲0 · 5重量份、經硼換算爲0.5重量份（實施例1 3 )，經 磷換算爲0.5重量份、經硼換算爲2.5重量份（實施例14) ’經磷換算爲〇 · 5重.量份、經硼換算爲5.0重量份（實施例 15 )，經磷換算爲2.5重量份 '經硼換算爲〇 . 5重量份（實 施例16 )，經磷換算爲2_5重量份、經硼換算爲5.0重量份 (實施例17 )，經磷換算爲5.0重量份、經硼換算爲〇.5重 量份（實施例1 8 ) ’經磷換算爲0.5重量份、經硼換算爲 2·5重量份（實施例19 )，經磷換算爲5.0重量份、經硼換 -18- 201115814 算爲5.0重量份（實施例20 )，除此之外，其他進行與實 施例5相同之操作而得鋰蓄電池。此外，係與實施例1相同 來調查放電特性。結果如第2表所示。 201115814 【1-I谳】 5.0mA/cm2 維持率(％) 66.3 38.3 76.5 74.0 I 76.5 65.3 62.2 54.6 81.1 77.9 68.1 52.3 63.5 63.6 75.8 82.1 68.4 56.3 68.2 66.7 80.6 86.3 76.6 66.8 2.5mA/cm2 維持率(％) 73.1 I 63.1 84.4 79.6 84.4 70.3 72.8 71.6 87.1 83.8 76.9 o 76.8 79.4 84.4 88.0 83.7 78.6 81.0 81.1 88.8 92.2 86.7 81.3 2 0.5mA/cm 維持率(％) 91.0 1 87.6 93.2 I_9L4__I 93.2 76.1 93.3 90.0 100.3 96.2 94.4 92.5 92.6 93.1 95.3 96.6 95.9 93.7 93.7 94.1 98.1 97.1 95.8 94.4 初期效率 (%) 80.3 CO ύ 80.1 79.0 77.8 I I 76.6__ I 73.7I 83.3 83.5 83.7 82.1 80.5 83.9 86.7 86.2 84.3 84.8 84.0 87.6 86.3 85.6 84.9 84.4 83.8 放電容量 (mAh/g) 1 524 | ιο CO lO 483 450 卜 寸 CO 另 I 445 I CO Ο CO CO CO CSI CO I 296 ! 388 I 353 I 360 305 σ> 〇g 寸 I 325 I σ> CO I 313 I 286 258 輸出特性 (W) 1 10-4 I 00 in Ί— I 11-4 I I 12.0 I I 10·4 I I 10-6 I 卜 00 I 13.0 I I 12.6 I I 11-2 I 00 od p T* i 10-5 I I 12-8 I I 13.7 丨 I 11-7 I 卜 ai 丨 12.0 I I 114 I l 13.8 I 14.8 I 13.2 11.4 DOD:50 (V) 0.66 ! I 0.79 I I 0-75 I I 0-71 I I 0-67 I 0.63 I 0.38 I I 0.63 I I 0.60 I 丨 0.57 I I 0.50 I I 0.43 I I 0.35 I I 0.49 I 丨 0.43 I 丨 0.47 I I 0-37 | I 0.35 I I 0.29 I 0.39 I 0.38 I I 0-37 | 0.36 0.35 燒結溫度 (°C)_ 〇 〇> 1,000 1100 1,200 硼化合物 (重量份） 〇 o i〇 in csi in CO ιο 〇 〇 in in csi in CO m o o IT> in cvi in CO l〇 o o l〇 l〇 csi in CO in 磷化合物 (重量份） 〇 in ir> c6 in csi io ο 〇 in in ci in csi in o o to ιο CO in csi i〇 o o m to CO l〇 oi l〇 o 生焦炭 (重量份） 100 5 鎰 <N J-X i 闺 in (N :辑 c〇 闺 1¾ cn AJ -1Λ 寸 U-1 .饈 I實施例4 辑 IK v〇 VO ϋ 卜 oo 卜 :辑 00 驷 ON 闺 in Os ΛΛ o S H 5 o 瘥 _ 瘥 fa CM i 堤 ί-10-201115814 The operation of adding a phosphorus compound or the like can simplify the entire production steps of the negative electrode active material for a lithium secondary battery. However, the first addition method and the second addition method differ in the production steps of the negative electrode active material for a lithium secondary battery by the specific method of addition, and the output characteristics or discharge capacity of the negative electrode active material itself for a lithium secondary battery. The initial efficiency and capacity retention rate are almost unchanged. The amount of the phosphorus compound to be added is preferably 0.1 to 6.0 parts by weight, more preferably 0.5 to 5.0 parts by weight, based on the weight of the raw coke 1 〇 煤 of the coal or the like. When the amount of addition is less than the lower limit, the effect of adding a phosphorus compound may be insufficiently obtained. On the other hand, when the amount of addition exceeds the upper limit, the low crystallization of the surface of the coke is delayed, and the output characteristics are lowered. In addition, the amount of the boron compound to be added is preferably 0.1 to 6.0 parts by weight, more preferably 0.5 to 5.0 parts by weight, based on 100 parts by weight of the raw coke, such as coal. When the amount of addition does not reach the lower limit, the effect of adding a boron compound may not be sufficiently obtained. On the other hand, when the amount added exceeds the upper limit, there is a fear that carbonization of coke is excessively promoted, and unreacted boron remains, and There is a concern that the output characteristics, the discharge capacity, and the initial efficiency 'capacity retention rate' of the negative electrode active material for a lithium secondary battery are deteriorated. The phosphorus compound is preferably a phosphoric acid from the viewpoint of being easily prepared into an aqueous solution and having high safety. The phosphoric acid is preferably a phosphoric acid (orthophosphoric acid), but is not limited thereto, and can be appropriately selected from linear polyphosphoric acid or cyclic polyphosphoric acid or various phosphate compounds. These phosphoric acids may be used alone or in combination of two or more. 5-11 - 201115814 Further, it is preferable to use boron carbide (b4c) as the above boron compound. In this case, even if the boron carbide is decomposed during sintering, the components obtained by the decomposition thereof are only the carbon of the constituent elements of the coke for the purpose of achieving the object of the present invention and the base material of the negative electrode activating material, and do not contain other components. Therefore, the adverse effects of the other components on the negative electrode activating substance can be suppressed. This coke is sintered. The sintering temperature can be set to a maximum temperature of 800 ° C or more and 1400 ° C or less. It is preferably in the range of 900 ° C to 1200 ° C, more preferably in the range of 900 ° C to 1 100 ° C. When the sintering temperature exceeds the upper limit, the crystal growth of the coke material is excessively promoted, and the output characteristics, the discharge capacity, the initial efficiency, and the capacity retention rate of the negative electrode active material for a lithium secondary battery are deteriorated, and the mass productivity is also considered. It is also not good. On the other hand, when the sintering temperature is lower than the lower limit, not only the sufficient crystal growth cannot be performed, but also the effect of adding the phosphorus compound and the boron compound is insufficient during the carbonization of the coke, and the negative electrode active material for the lithium secondary battery is used. The output characteristics, discharge capacity, initial efficiency, and capacity retention rate are degraded. Further, the holding time at the highest reaching temperature is not particularly limited, but is preferably 30 minutes or longer. Further, the sintering atmosphere gas is not particularly limited, and may be an inert gas such as argon gas or nitrogen gas, or a non-oxidizing gas atmosphere in a non-sealed state such as a rotary kiln, or a closed state like a Riedhammer furnace. Non-oxidizing gas environment>> When a lithium secondary battery is constructed using the negative electrode active material of the present invention, a lithium-containing transition metal oxide LiM ( 1 ) x 〇 2 can be used for the corresponding positive electrode (where X is OSxSl) In the formula, M(l) represents a transition metal, which is composed of at least one of Co, Ni, Mn, Ti, Cr, V, Fe, Zn, and A1 201115814, Sn, and In), LiM (1) yM ( 2 ) 2.y〇4 (where y is the number of the range of OSySl, where M(l) and M(2) represent transition metals, which are Co, Ni, Μη, Ti , at least one of Cr, V, Fe, Zn, Al, Sn, and In), transition metal chalcogenide (Ti, S2, NbSe, etc.), vanadium oxide (V205, V6013, V2〇4, V306, etc.) And lithium compounds, generally SMxMo6Ch6-y (where x is 0$ xS4, y is the number in the range of OSySl, where Μ represents a metal based on transition metals Ch represents a sulfur metals) represented by the Xiefuleier phase (Chevrel Phase) compounds, or activated carbon, activated carbon fiber, etc. The positive electrode active material. Further, any of the conventionally known electrolytes may be used as the electrolyte between the positive electrode and the negative electrode, and examples thereof include LiC104, LiBF4, LiPF6, LiAsF6' LiB (C6H5), LiCl, LiBr, Li3S03, and Li (CF3SO2). 1N or 2 of 2N ' Li ( CF3SO2 ) 3C, Li ( CF3CH2OSO2 ) 2N ' Li ( CF3CF2CH2OSO2 ) 2N, Li ( HCF2CF2CH2OSO2 ) 2N ' Li ( ( CF3 ) 2CHOSO2 ) 2N, LiB [C6H3(CF3) 2]4 a mixture of the above. Further, as the nonaqueous electrolyte, for example, propylene carbonate, ethylene carbonate, butylene carbonate, vinyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,1-dimethoxy can be used. Ethylethane, 1,2-dimethoxyethane, 1,2-diethoxyethane 'butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl N-1,3-dioxolane, methoxybenzene, diethyl ether, cyclopentane, methylcyclobutyl hydrazine, acetonitrile, chloronitrile, propionitrile, trimethyl borate, tetramethyl decanoate Methane, dimethylformamide, -13- 201115814 N-methylrrolidone, ethyl acetate, trimethyl orthoformate, nitrobenzene, benzamidine chloride, benzamidine bromide, tetrahydrothiophene, A single solvent such as dimethyl sulfoxide, 3-methyl-2 oxazolidinone, ethylene glycol, sulfurous acid or dimethylsulfuric acid or a mixed solvent of two or more kinds. When the negative electrode active material is used to form the negative electrode, fluorine-based resin powder such as polyvinylidene fluoride (PVDF), polyethylenimine (PI) resin, styrene butadiene rubber (SBR), or carboxy is generally used. A water-soluble binder such as methyl cellulose (CMC) is a carbonaceous binder, and the binder is mixed with a solvent such as N-methylrrolidone (NMP), dimethylformamide or water or an alcohol. This is carried out by forming a slurry together with the above negative electrode active material, and then applying it to a current collector and drying it. [Examples] Hereinafter, the present invention will be more specifically described based on examples. However, the content of the present invention is not limited to the embodiments. (Example 1) A purified coke obtained by removing a quinoline insoluble fraction from a coal-based heavy oil was subjected to heat treatment at a temperature of 500 ° C for 24 hours by a delayed coking method to obtain a produced coke (raw coke). The fine coke powder having an average particle diameter of 9.9 μm was obtained by fine pulverization and granulation by a jet mill. Phosphate ester (I. 4 mass% active phosphorus solid resin: HCA manufactured by Sanko Co., Ltd., chemical name: 9,10-dihydro-9- evil) was added to 1 part by weight of the raw coke powder obtained above. -10-phosphaphene-10-oxide) 201115814 25·0 parts by weight (calculated by phosphorus: 35 parts by weight), and boron carbide I" parts by weight (calculated in terms of boron: 1.25 parts by weight). The above-mentioned coke material made of phosphoric acid ester and boron carbide is heated from room temperature at a rate of 600 ° C / hour, reaches 9 〇 < rc (maximum temperature reached), and is further maintained for 2 hours for carbonization (sintering) Then, a negative electrode active material for a lithium secondary battery is used. Then, 5% by mass of polyvinylidene fluoride (made by PVDF 'Kureha Co., Ltd.) as a binder is added to the negative electrode active material for a lithium secondary battery, and N-methylrrolidone ( NMP) was kneaded as a solvent to prepare a slurry. This was uniformly applied to a copper foil having a thickness of 18 μm to obtain a negative electrode foil. The negative electrode foil was dried and molded to have a predetermined current density to produce a negative electrode foil. Electrode sheet from which the sheet A circular electrode having a diameter of 15 mm (D) was cut to prepare a negative electrode. In order to evaluate the electrode characteristics under the single pole of the negative electrode, a lithium metal having a cut of 15.5 mm (D was used as a counter electrode). Dissolving 1^??6 in a mixed solvent of ethylene carbonate and diethyl carbonate (mixed in a volume ratio of 1:1) at a concentration of 1 mol/Ι as an electrolyte, and using a porous membrane of propylene as a separator To produce a coin cell, a lithium battery was produced. At a constant temperature of 25 ° C, 5 mA/cm 2 was implemented in a voltage range in which the lower limit voltage of the terminal voltage was set to 0 V and the upper limit voltage of the discharge was set to 1.5 V. The constant current discharge was measured and the discharge characteristics at this time were investigated. The results are shown in Table 1. (Examples 2 to 3) In Example 1, the amount of the phosphate added and the amount of boron carbide were -15 - 201115814, converted to 3.5 parts by weight in terms of phosphorus, 1.5 parts by weight in terms of boron, 2.5 parts by weight in terms of phosphorus, 2.5 parts by weight in terms of boron, and 1.5 parts by weight in terms of phosphorus, converted in terms of boron 3) Example 3), otherwise, the same as Example 1 | The lithium battery was the same as in Example 1. The results of the investigation were as shown in Table 1. (Comparative Example 1) Using 100 parts by weight of coke material of raw coke powder and less than boron carbide, the other was carried out. The lithium battery was obtained in the same manner as in Example 1. The results of the investigation are shown in Table 1. (Comparative Example 2) 100 parts by weight of coke ash material of raw coke powder was used and only 5.0 parts by weight was used. Other than the above, the same operation was carried out to obtain a lithium secondary battery. In addition, the discharge characteristics were examined by the examples and the results are shown in Table 1. (Comparative Example 3) A lithium secondary battery was obtained by performing the same operation except that 100 parts by weight of the coke material of the raw coke powder was used and only 5.0 parts by weight of boron carbide was used. In addition, the discharge characteristics were examined in the examples and examples. The results are shown in Table 1. t parts, changed (Example 2 5 parts by weight (0 operation and electrical characteristics. Phosphate addition operation and electrical characteristics. $ plus phosphorus exchange is the same as in Example 1 1 to adjust the boron exchange with the example 1 1 is the same as the adjustment-16-201115814 (Examples 4 to 6) In the embodiment, the sintering temperature (the highest temperature reached) of the coke material is changed from 90 (TC to 10 °C). Other lithium batteries were obtained in the same manner as in Examples 1 to 3. The discharge characteristics were examined in the same manner as in Example i. The results are shown in Table 1. (Comparative Examples 4 to 6) Comparative Examples 1 to 3 In the middle of the process, the sintering temperature (the highest temperature reached) of the coke material was changed from 900 C to 1000 C, and the lithium battery was obtained by the same operation as in Comparative Examples 1 to 3, respectively. The discharge characteristics were examined. The results are shown in Table 1. (Examples 7 to 9) In Examples 1 to 3, the sintering temperature (maximum reaching temperature) of the coke material was changed from 900 ° C to 11 ° C. 'Other than this, the other operations were the same as those of the first to third embodiments to obtain lithium storage. Further, the discharge characteristics were examined in the same manner as in Example J. The results are shown in Table 1. (Comparative Examples 7 to 9) In Comparative Examples 1 to 3, the sintering temperature (maximum reaching temperature) of the coke material was changed from 900. The lithium battery was obtained in the same manner as in Comparative Examples 1 to 3 except that the temperature was changed to 1100 ° C. The discharge characteristics were examined in the same manner as in Example 1. The results are shown in Table 1. -17-201115814 (Examples 10 to 12) In Examples 1 to 3, the sintering temperature (maximum reaching temperature) of the coke material was changed from 90 〇 ° C to 1 200. (:, other than this, Lithium storage batteries were obtained in the same manner as in Examples 1 to 3. The discharge characteristics were examined in the same manner as in Example 1. The results are shown in Table 1 (Comparative Examples 10 to 12) In Comparative Examples 1 to 3 A lithium secondary battery was obtained by performing the same operations as in Comparative Examples 1 to 3, except that the sintering temperature (maximum reaching temperature) of the coke material was changed from 900 ° C to 1 200 ° C. Example 1 The discharge characteristics were investigated in the same manner. The results are shown in Table 1. (Examples) 13 to 20) In Example 5, the amount of the phosphate ester to be added and the amount of boron carbide were changed to 2·5 parts by weight in terms of phosphorus conversion and boron conversion, and converted to 0. 5 by weight in terms of phosphorus. 0.5 parts by weight of boron (Example 13), 0.5 parts by weight in terms of phosphorus, and 2.5 parts by weight in terms of boron (Example 14) 'In terms of phosphorus, it is 〇·5 weight. 5.0 parts by weight of boron (Example 15), converted to 2.5 parts by weight in terms of phosphorus, in terms of boron, 5 parts by weight (Example 16), 2 to 5 parts by weight in terms of phosphorus, and 5.0 parts by weight in terms of boron. (Example 17), 5.0 parts by weight in terms of phosphorus, and 0.5 parts by weight in terms of boron (Example 18) '0.5 parts by weight in terms of phosphorus, and 2.5% by weight in terms of boron (Example) 19) A lithium secondary battery was obtained in the same manner as in Example 5 except that the amount of phosphorus was 5.0 parts by weight and the boron was changed to -18 to 201115814 (Example 20). Further, the discharge characteristics were examined in the same manner as in the first embodiment. The results are shown in Table 2. 201115814 [1-I谳] 5.0mA/cm2 Maintenance rate (%) 66.3 38.3 76.5 74.0 I 76.5 65.3 62.2 54.6 81.1 77.9 68.1 52.3 63.5 63.6 75.8 82.1 68.4 56.3 68.2 66.7 80.6 86.3 76.6 66.8 2.5mA/cm2 Maintenance rate (%) 73.1 I 63.1 84.4 79.6 84.4 70.3 72.8 71.6 87.1 83.8 76.9 o 76.8 79.4 84.4 88.0 83.7 78.6 81.0 81.1 88.8 92.2 86.7 81.3 2 0.5 mA/cm Maintenance rate (%) 91.0 1 87.6 93.2 I_9L4__I 93.2 76.1 93.3 90.0 100.3 96.2 94.4 92.5 92.6 93.1 95.3 96.6 95.9 93.7 93.7 94.1 98.1 97.1 95.8 94.4 Initial efficiency (%) 80.3 CO ύ 80.1 79.0 77.8 II 76.6__ I 73.7I 83.3 83.5 83.7 82.1 80.5 83.9 86.7 86.2 84.3 84.8 84.0 87.6 86.3 85.6 84.9 84.4 83.8 Discharge capacity (mAh/g 1 524 | ιο CO lO 483 450 卜寸 CO I 445 I CO Ο CO CO CO CSI CO I 296 ! 388 I 353 I 360 305 σ> 〇g inch I 325 I σ> CO I 313 I 286 258 Output characteristics (W) 1 10-4 I 00 in Ί—I 11-4 II 12.0 II 10·4 II 10-6 I 00 I 13.0 II 12.6 II 11-2 I 00 od p T* i 10-5 II 12- 8 II 13.7 丨I 11-7 I 卜 丨 2.012.0 II 114 I l 13.8 I 14.8 I 13.2 11. 4 DOD:50 (V) 0.66 ! I 0.79 II 0-75 II 0-71 II 0-67 I 0.63 I 0.38 II 0.63 II 0.60 I 丨0.57 II 0.50 II 0.43 II 0.35 II 0.49 I 丨0.43 I 丨0.47 II 0 -37 | I 0.35 II 0.29 I 0.39 I 0.38 II 0-37 | 0.36 0.35 Sintering temperature (°C)_ 〇〇> 1,000 1100 1,200 Boron compound (parts by weight) 〇oi〇in csi in CO ιο 〇〇in in Csi in CO moo IT> in cvi in CO l〇ool〇l〇csi in CO in phosphorus compound (parts by weight) 〇in ir> c6 in csi io ο 〇in in ci in csi in oo to ιο CO in csi i〇 Oom to CO l〇oi l〇o raw coke (parts by weight) 100 5 镒<N JX i 闺in (N: series c〇闺13⁄4 cn AJ -1Λ inch U-1 .馐I Example 4 Series IK v 〇 VO ϋ oo 卜: 00 驷 ON 闺 in Os ΛΛ o SH 5 o 瘥 _ 瘥 fa CM i ί
-20- 201115814 5.0mA/cm2 維持率(％) 62.2 76.5 I 72.4 68.3 73.1 I 77.9 82.1 81.3 75.8 61.6 2.5mA/cm2 維持率(％) 72.8 83.0 81.6 80.3 82.0 83.8 88.0 88.4 84.4 80.0 0.5mA/cm2 維持率(％) 93.3 96.7 97.6 98.5 97.3 96.2 96.6 97.4 95.3 ! 94.1 初期效率 (%) 73.7 82.4 82.2 81.9 82.8 83.7 84.3 85.0 86.2 '83.9 放電容量 (mAh/g) 303 364 ΙΟ CO 00 CO 396 406 CO OO I 388 I I 353 I 296 輸出特性 (W) 10.6 丨 12.7 | I 11·9 I CSJ •r- OO r— 1 12.6 i L 13.5 I l 13.5 I I 13.0 I 10.6 DOD:50 (V) I 0.38 I I 0.48 I 丨 0.51 I I 0.53 I I 0.55 I I 0-57 I I 0.50 I 0.49 I 0.38 I I 0.35 I 燒結溫度 CC) 1000 硼化合物 讎份） 〇 in 〇 in Csj o iri in d Csj o in IO in csi o iri 磷化合物 (重量份） 〇 m ο in in m oi in CM· m cvi 〇 iri o iri o iri 生焦炭 (重量份） 〇 CO 逞 fi 寸 5 瘥 M- ps Ϊ 闺 綱 獅 i 据 OO Ϊ 瘥 .御 i 崔 _ 瘥 驷-20- 201115814 5.0 mA/cm2 Maintenance rate (%) 62.2 76.5 I 72.4 68.3 73.1 I 77.9 82.1 81.3 75.8 61.6 2.5 mA/cm2 Maintenance rate (%) 72.8 83.0 81.6 80.3 82.0 83.8 88.0 88.4 84.4 80.0 0.5 mA/cm2 Maintenance rate (%) 93.3 96.7 97.6 98.5 97.3 96.2 96.6 97.4 95.3 ! 94.1 Initial efficiency (%) 73.7 82.4 82.2 81.9 82.8 83.7 84.3 85.0 86.2 '83.9 Discharge capacity (mAh/g) 303 364 ΙΟ CO 00 CO 396 406 CO OO I 388 II 353 I 296 Output characteristics (W) 10.6 丨12.7 | I 11·9 I CSJ •r- OO r— 1 12.6 i L 13.5 I l 13.5 II 13.0 I 10.6 DOD:50 (V) I 0.38 II 0.48 I 丨0.51 II 0.53 II 0.55 II 0-57 II 0.50 I 0.49 I 0.38 II 0.35 I Sintering temperature CC) 1000 Boron compound )) 〇in 〇in Csj o iri in d Csj o in IO in csi o iri Phosphorus compound (parts by weight) 〇 m ο in in m oi in CM· m cvi 〇iri o iri o iri raw coke (parts by weight) 〇CO 逞fi inch 5 瘥M- ps Ϊ 闺 lion i According to OO Ϊ 瘥.御i 崔 _ 瘥驷
C -21 - 201115814 從第1表及第2表中可得知，在依循本發明將生焦炭粉 中添加有磷酸酯與碳化硼之焦炭材料進行燒結所得之實施 例的鋰蓄電池用負極活性物質中，其輸出特性、放電容量 、初期效率及容量維持率的性能均衡性佳。尤其將該添加 量設定爲相對於生焦炭100重量份而言，以經磷及硼換算 分別爲0.5重量份〜5·0重量份的比率來添加，可製得顯示出 輸出特性（W)爲10W以上，放電容量（mAh/g)爲280 ( mAh/g )以上，初期效率（％ )爲75 ( 〇/〇 )以上，以及容量 維持率（％ )爲6 8 ( % )以上之良好的放電特性之鋰蓄電 池的負極材料用碳材料（鋰蓄電池用負極活性物質）。 比較例1、4、7、1 0，爲使用僅由生焦炭粉所構成之 焦炭材料者’其容量維持率與依循本發明之實施例相比， 該特性在各燒結溫度中均較差。尤其在燒結溫度爲i 〇〇〇。〇 以下時，雖然放電容量（mAh/g)爲280 ( mAh/g)以上， 但輸出特性（W )與依循本發明之實施例相比更爲降低， 可得知其作爲鋰蓄電池的負極材料用碳材料之特性的均衡 性差。此外，燒結溫度爲1200。(：以上時，雖然輸出特性（ W)爲10W以上，但放電容量（mAh/g )未達280 (mAh/g )’可得知其作爲鋰蓄電池的負極材料用碳材料之特性的 均衡性差。 此外，比較例2、5、8、1 1，爲僅將磷化合物添加於 生焦炭粉者’其容量維持率與依循本發明之實施例相比， 在各燒結溫度中均較差。尤其在燒結溫度爲1100°c以下時 ，輸出特性（W )未達1 1 W，與依循本發明之實施例相比C-21 - 201115814 It is known from the first table and the second table that the negative electrode active material for lithium battery of the embodiment obtained by sintering the coke material containing phosphoric acid ester and boron carbide in the raw coke powder according to the present invention Among them, the performance characteristics, discharge capacity, initial efficiency, and capacity retention ratio are well balanced. In particular, the addition amount is set to be 100 parts by weight of raw coke, and is added in a ratio of 0.5 parts by weight to 0.5 parts by weight in terms of phosphorus and boron, and the output characteristic (W) is obtained. 10W or more, the discharge capacity (mAh/g) is 280 (mAh/g) or more, the initial efficiency (%) is 75 (〇/〇) or more, and the capacity retention rate (%) is 6 8 (%) or more. A carbon material (a negative electrode active material for a lithium secondary battery) for a negative electrode material of a lithium secondary battery having a discharge characteristic. In Comparative Examples 1, 4, 7, and 10, the capacity retention ratio of the coke material composed only of the raw coke powder was inferior to the examples according to the present invention, and the characteristics were inferior in the respective sintering temperatures. Especially at the sintering temperature i 〇〇〇. In the following case, although the discharge capacity (mAh/g) is 280 (mAh/g) or more, the output characteristic (W) is further lowered as compared with the embodiment according to the present invention, and it can be known as a negative electrode material of a lithium secondary battery. The balance of the characteristics of the carbon material is poor. Further, the sintering temperature was 1200. (In the above case, although the output characteristic (W) is 10 W or more, the discharge capacity (mAh/g) is less than 280 (mAh/g)', and it is known that the balance of the characteristics of the carbon material for the negative electrode material of the lithium secondary battery is poor. Further, Comparative Examples 2, 5, 8, and 1 are those in which only the phosphorus compound is added to the raw coke powder, and the capacity retention ratio thereof is inferior to each of the sintering temperatures as compared with the examples according to the present invention. When the sintering temperature is 1100 ° C or less, the output characteristic (W ) is less than 1 1 W, compared with the embodiment according to the present invention.
-22- 201115814 ，可得知該特性的均衡性差。 此外，比較例3、6、9、12，爲僅將硼化合物添加於 生焦炭粉者，其容量維持率與依循本發明之實施例相比’ 在各燒結溫度中均較差。尤其在燒結溫度爲1 1 〇〇°C以下時 ，雖然放電容量（mAh/g)爲280 (mAh/g)以上’但輸出 特性（W )與依循本發明之實施例相比更爲降低，可得知 其作爲鋰蓄電池的負極材料用碳材料之特性的均衡性差。 (實施例2 1 ) 係將製作負極電極箔時所用之黏合劑，從聚偏二氟乙 烯變更爲聚醯亞胺樹脂（宇部興產公司製），除此之外’ 其他與實施例2相同而製作出鋰蓄電池。此外，係與實施 例1相同來調查放電特性。結果如第3表所示。爲了進行比 較，亦將實施例2之結果一同顯示於第3表。 (實施例22 ) 係將製作負極電極箔時所用之黏合劑，從聚偏二氟乙 烯變更爲聚醯亞胺樹脂（宇部興產公司製），除此之外， 其他與實施例5相同而製作出鋰蓄電池。此外，係與實施 例1相同來調查放電特性。結果如第3表所示。爲了進行比 較’亦將實施例5之結果一同顯示於第3表。 (實施例2 3 ) 係將製作負極電極箔時所用之黏合劑，從聚偏二氟乙 5 -23- 201115814 烯變更爲聚醯亞胺樹脂（宇部興產公司製），除此之外， 其他與實施例8相同而製作出鋰蓄電池。此外，係與實施 例1相同來調查放電特性。結果如第3表所示。爲了進行比 較，亦將實施例8之結果一同顯示於第3表。 -24- 201115814 【ε谳】 5.0mA/cm2 維持率(％) L 74.0 I 丨 76.9 I I 77.9 I 丨 84.0 I 82.1 88.5 2.5mA/cm2 維持率(％) 179.6 1 82.7 L 83.8 87.1 88.0 91.4 0.5mA/cm2 S： Μ I__914__I 95.0 | 96.2 I 98.1 96.6 98.6 锬 踩 g 1 79.0 1 I 77.4 | I 83.7 I I 82.0 | 丨 84.3 I | 82.6 | I放電容_ (mAh/g) 1 483 1 I 473 | | 406 I | 398 | I 360 I I 352 I 輸出特性 /—s 丨.11.4 I I 11.7 I 丨.12.6 I 丨 13.3 | I 13-7 I I 14.5 I 〇 Q I 0-71 I I 0 77 I I 0-57 | | 0.63 I I 0 47 I | 0.53 I m < I Ipvdf Q： PVDF E PVDF Q： m m 遐 趣 /—s P V—✓ 900 1000 1100 <π 蔭 _ tlmll B in c\i <Π k重量份)j m csi 生焦1 _ ΡΠ| 100 潛 s iW B 100 |實施例21| (N 堤 IK I實施例妇 wn in 實施例23 實施例8 s 25 201115814 從第3表中可得知，在將從鋰蓄電池用負極活性物質 中製作出負極電極時所使用之黏合劑，從聚偏二氟乙烯變 更爲聚醋亞胺時’DOD (放電深度：Depth of Discharge) :5 0亦爲非常小的値，可得知其輸出特性增大。亦即，由 上述負極材料用碳材料所構成之上述負極電極的實質電位 降低，上述蓄電池的實質電池電壓上升，而使輸出特性增 大。 此外，可製得顯示出輸出特性（W)爲11W以上，放 電容量（mAh/g )爲350 ( mAh/g )以上，初期效率（％ ) 爲77 ( % )以上，以及容量維持率（％ )爲76 ( % )以上之 良好的放電特性之鋰蓄電池的負極材料用碳材料（鋰蓄電 池用負極活性物質）。 另一方面，從第3表中可得知，當製作鋰蓄電池的負 極電極時所使用之黏合劑爲聚醯亞胺時，與黏合劑爲聚偏 二氟乙烯時相比，可得知其DOD (放電深度：Depth of Discharge) : 50降低，而使輸出特性（W)提升。此外， 容量維持率（％ )亦有所提升。關於藉由變更此般黏合劑 的種類使蓄電池的放電特性產生變化之原因，目前仍未明 瞭。 以上係根據上述具體例來詳細說明本發明，但本發明 並不限定於上述具體例，在不脫離本發明之範疇內，可進 行各種變形及變更。 -26--22- 201115814 , we can know that the balance of this feature is poor. Further, in Comparative Examples 3, 6, 9, and 12, in which only the boron compound was added to the raw coke powder, the capacity retention ratio was inferior to that in the respective sintering temperatures as compared with the examples according to the present invention. In particular, when the sintering temperature is 1 1 〇〇 ° C or less, although the discharge capacity (mAh/g) is 280 (mAh/g) or more, the output characteristic (W) is further lowered as compared with the embodiment according to the present invention. It is known that the balance of the characteristics of the carbon material for the negative electrode material of the lithium secondary battery is poor. (Example 2 1) The binder used in the production of the negative electrode foil was changed from polyvinylidene fluoride to polyimide resin (manufactured by Ube Industries, Ltd.), and otherwise the others were the same as in Example 2. And made a lithium battery. Further, the discharge characteristics were examined in the same manner as in the first embodiment. The results are shown in Table 3. For comparison, the results of Example 2 are also shown together in Table 3. (Example 22) The same procedure as in Example 5 except that the binder used in the production of the negative electrode foil was changed from polyvinylidene fluoride to polyimine resin (manufactured by Ube Industries, Ltd.). Create a lithium battery. Further, the discharge characteristics were examined in the same manner as in the first embodiment. The results are shown in Table 3. The results of Example 5 are also shown in Table 3 for comparison. (Example 2 3) The binder used in the production of the negative electrode foil was changed from polyvinylidene fluoride 5 -23- 201115814 olefin to poly phthalimide resin (manufactured by Ube Industries, Ltd.). A lithium secondary battery was produced in the same manner as in Example 8. Further, the discharge characteristics were examined in the same manner as in the first embodiment. The results are shown in Table 3. For comparison, the results of Example 8 are also shown together in Table 3. -24- 201115814 [ε谳] 5.0mA/cm2 Maintenance rate (%) L 74.0 I 丨76.9 II 77.9 I 丨84.0 I 82.1 88.5 2.5mA/cm2 Maintenance rate (%) 179.6 1 82.7 L 83.8 87.1 88.0 91.4 0.5mA/ Cm2 S: Μ I__914__I 95.0 | 96.2 I 98.1 96.6 98.6 锬 step g 1 79.0 1 I 77.4 | I 83.7 II 82.0 | 丨84.3 I | 82.6 | I discharge capacitor _ (mAh/g) 1 483 1 I 473 | | 406 I | 398 | I 360 II 352 I Output Characteristics /—s 丨.11.4 II 11.7 I 丨.12.6 I 丨13.3 | I 13-7 II 14.5 I 〇QI 0-71 II 0 77 II 0-57 | | 0.63 II 0 47 I | 0.53 I m < I Ipvdf Q: PVDF E PVDF Q: mm Interest /—s PV—✓ 900 1000 1100 <π shade _ tlmll B in c\i <Π k parts by weight) jm csi Coke 1 _ ΡΠ | 100 s s iW B 100 | Example 21 | (N ike I IK I embodiment wn in Example 23 Example 8 s 25 201115814 It can be seen from Table 3 that it will be used from a lithium battery The binder used in the preparation of the negative electrode in the negative electrode active material is changed from polyvinylidene fluoride to polyacetamide. 'DOD (Depth of Discharge): 50 is also very In the case of a small enthalpy, the output characteristics of the negative electrode formed of the carbon material for a negative electrode material are lowered, and the substantial battery voltage of the battery is increased to increase the output characteristics. It can be obtained that the output characteristic (W) is 11 W or more, the discharge capacity (mAh/g) is 350 (mAh/g) or more, the initial efficiency (%) is 77 (%) or more, and the capacity retention rate (%). A carbon material (a negative electrode active material for a lithium secondary battery) for a negative electrode material of a lithium secondary battery having a good discharge characteristic of 76 (%) or more. On the other hand, it can be seen from the third table that when a negative electrode of a lithium secondary battery is fabricated When the binder used is polyimine, it is known that the DOD (Depth of Discharge): 50 is lowered, and the output characteristic (W) is improved, compared with when the binder is polyvinylidene fluoride. . In addition, the capacity retention rate (%) has also increased. It is still unclear why the discharge characteristics of the battery are changed by changing the type of the binder. The present invention has been described in detail above with reference to the specific embodiments described above, but the present invention is not limited to the specific examples described above, and various modifications and changes can be made without departing from the scope of the invention. -26-