1287890 玖、發明說明Λ 【發明所屬之技術領域】 本發明係關於一種鐘二次電池的負型活 製備方法。詳言之，係關於一種鋰二次電池 電容及極佳放電/充電效率的陽極活性材料， 【先前技術】 石厌系材料主要係作為鐘二次電池的陽極 是，由碳製成的陽極所能表現出的最大理1 327 mAh/g (844 mAh/cc)，因此限制 了其電 的可此性被研發作為陽極材料的鐘金屬， 密度，一直被認為可實現高電容量的目的， 的相關問題，肇因於隨著電池被重複充電/放 狀結晶的生長（growth of dendrities)及較短t 期哥命專問題。 此外’有許多研究建議以鋰合金作為一 之链金屬的替代材料。矽藉由與鋰之間的反 吸留與釋出鋰，且具有一最大約4〇2〇 mAh/cc，比重約2·23)的理論電容值，係遠 論電容值高出許多，因此是一種潛在的高電 但是’在電池充電/放電時，矽因為與鋰反應 而谷易出現碎裂的情況，因而破壞石夕活性材 當重複充電/放電時，電池電容會驟然下降因 性材料及其之 用之具高可逆 及其之製備方 活性材料。但 倉電容量只有 容量往上增加 因具有高能量 但卻有安全性 電所致之樹枝 0充電/放電週 種具高電容量 應能夠可逆的 mAh/g (9800 較碳材料的理 容陽極材料。 導致體積改變 顆粒。為此， 而降低其充電 1287890 /放電週期的壽命。 為克服前述問題，已有人裎ψ ia ^ 句人梃出由一可與鋰反應的活性 相興一不會與鋰反應的非 祖, 性相組合而成的複合活性材 料’但迄今尚未有人建議I 人 ^. /、有 化合物組成且可使所用 材枓發揮最大效能之可供非溶 1¾托44· , , 土电解質系一次電池用的 陽極材料，及製備該陽極材料的方法。 【發明内容】 〜本發明係為了解決上㈣題而提出，因此本發明一目的 係提供一種供一非溶液型電解 a 貝糸一一人電池用的陽極活性 二其具有一高的鐘-吸留與釋出量，因此當作為-非溶 液型電解質系二次電池用的陽極活性材料，可達到高充 電’放電容量，初始不可逆電容的少量損失及一極佳的充電 ’放電週期壽命；及製備該陽極活性材料的方法。 依捸本發明，可藉由提供一種鐘二次電池用的陽極活 性材料來達成上述及其他"，其包含一種由一超細石夕相 顆粒’ -環繞在該超細矽相顆粒的氧化物及_碳材料所組 成的複合物。 、依據本發明另-態樣，提供一種鐘二次電池用的陽極 活性材料’其包含一種由一超細矽相顆粒及一環繞在該超 細石夕相顆粒的氧化物所組成的複合物。 依據本發明另一態樣，提供一種製備鋰二次電池用的 陽極活性材料的方法，包含： 製備一種由一超細矽相顆粒及一環繞在該超細矽相顆 1287890 粒外的氧化物所組成的複合物，其係藉由藉由將二氧化矽 (SiOx)/、 種具有氧化物形成給（ΔΗ f〇r)之絕對值大於二 氧化石夕及一負型氧化物形成焓之材料混合在一起，以機械 化學方法或對其施以熱化學反應以還原二氧化矽的方式來 製備；及 混合該複合物與一碳材料。 依據本發明另一態樣，提供一種製備鋰二次電池用的 陽極活性材料的方法，包含： 種製備一由一超細矽相顆粒及一環繞在該超細矽相 顆粒的氧化物所組成之複合物的方法，其係藉由將二氧化 矽（Sl〇X)及一種具有氧化物形成焓（△ HfQr)之絕對值大於 一氧化石夕及負型氧化物形成焓之材料混合在一起，藉由一 機械化學方法或將其施以熱化學反應以還原二氧化矽的方 式來製備。 貝他万式 以下將詳細說明本發明。 本發明之陽極活性材料係由一超細矽相顆粒及一環卷 相顆粒的氧化物組成之複合物所構成，或“ =與碳材料組成的混合物所構成。上述氧化物是一淨 不…鋰發生反應的非反應性材料，爲能有效 制效應，較佳係將矽相顆粒的大小 矽相的分右可％丄擔#人 敢】化。思類精在 冑可4由機械5金或機械化學m法來 達成。依據本發明，㈣相顆粒係、為奈米等級的=致』 1287890 依據本發明，該陽極活性材料可藉由限制β ^ 列及減輕因該活 性材料與鋰反應後所致的體積變化，來防止兮、本^ 止名活性材料被機 械性破壞，藉以實現高電容與改善的充電/放電週期I命 現在，將詳細說明製備該陽極活性材料的方法。 一種内含超細矽顆粒及一環繞該超細矽顆粒的氧化物 的複合物係藉由將二氧化矽及一種具有氧化物形成焓（△ Hf0r)之絕對值大於該二氧化矽及一負型氧化物形成焓之 材料混合在一起’同時藉由一機械化學方法或對其施以熱 化學反應以還原二氧化矽的方式來製備。 該二氧化矽材料可為Si〇2、si〇、sizcKSiiSia3、1287890 发明 发明 发明 发明 发明 发明 Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ 。 。 。 。 。 。 。 。 。 。 。 。 。 In particular, it relates to an anode active material of a lithium secondary battery capacitor and an excellent discharge/charging efficiency. [Prior Art] A stone anodic material is mainly used as an anode of a clock secondary battery, and an anode made of carbon. The maximum performance of 1 327 mAh/g (844 mAh/cc) can be exhibited, thus limiting the electrical properties of the clock metal that has been developed as an anode material, and the density has been considered to achieve high capacitance. Related issues are due to the fact that the battery is recharged/growth of dendrities and shorter t-term comrades. In addition, many studies have suggested using lithium alloys as a substitute for chain metals.矽 By releasing and releasing lithium with lithium, and having a theoretical capacitance value of about 4〇2〇mAh/cc and a specific gravity of about 2·23), the value of the capacitance is much higher, so It is a potential high-power but 'when the battery is charged/discharged, the ruthenium is prone to fragmentation due to the reaction with lithium, thus destroying the Shixia active material when the charge/discharge is repeated, the battery capacitance will suddenly drop due to the material. And its use is highly reversible and its preparation of active materials. However, the capacity of the warehouse is only increased upwards due to the high energy but the safety of the branches. The charging/discharging of the branches is high. The high capacity should be reversible mAh/g (9800 is more suitable for carbon materials than anode materials). This causes the volume to change particles. To this end, it reduces the life of charging 1287890 / discharge cycle. In order to overcome the above problems, it has been known that the reaction of lithium can react with lithium without reacting with lithium. The non-progenitor, the composite composite material of the sexual phase' has not been suggested so far. I have a compound composition and can make the material used to maximize the effectiveness of the non-dissolving material. The invention relates to an anode material for a primary battery and a method for preparing the anode material. SUMMARY OF THE INVENTION The present invention is proposed to solve the above problem (4), and therefore an object of the present invention is to provide a non-solution type electrolysis a shellfish. The anode active for a human battery has a high clock-storage and release amount, so that when used as an anode active material for a non-solution type electrolyte secondary battery, high charge can be achieved. 'discharge capacity, small loss of initial irreversible capacitance and an excellent charge 'discharge cycle life; and a method of preparing the anode active material. According to the present invention, by providing an anode active material for a clock secondary battery Achieving the above and other "comprising a composite of an ultrafine smectite particle'-surrounding the oxide and _carbon material of the ultrafine 矽 phase particle. According to another aspect of the present invention, An anode active material for a clock secondary battery is provided which comprises a composite composed of an ultrafine 矽 phase particle and an oxide surrounding the ultrafine smectite particle. According to another aspect of the present invention, Provided is a method for preparing an anode active material for a lithium secondary battery, comprising: preparing a composite composed of an ultrafine 矽 phase particle and an oxide surrounding the ultrafine 矽 phase particle 1287890 By mixing cerium oxide (SiOx)/, a material having an oxide formation (ΔΗ f〇r) having an absolute value greater than that of the cerium oxide and a negative oxide forming cerium, Preparing a chemical method or applying a thermochemical reaction to reduce cerium oxide; and mixing the composite with a carbon material. According to another aspect of the present invention, an anode active material for preparing a lithium secondary battery is provided The method comprises: preparing a composite of an ultrafine 矽 phase particle and an oxide surrounding the ultrafine 矽 phase particle by using cerium oxide (Sl〇X) and A material having an oxide forming enthalpy (ΔHfQr) having an absolute value greater than that of a monocrystalline oxide and a negative oxide forming cerium, which is reduced by a mechanochemical method or by subjecting it to a thermochemical reaction to reduce cerium oxide The present invention will be described in detail below. The anode active material of the present invention is composed of a composite of an ultrafine 矽 phase particle and an oxide of a ring wound phase particle, or "= with carbon A mixture of materials consisting of. The above oxide is a non-reactive material which reacts with lithium. In order to be effective, it is preferable to divide the size of the 矽 phase particles into the right phase. The class is based on the mechanical 5 gold or mechanochemical m method. According to the present invention, the (four) phase particle system is nanometer grade = 1287890. According to the present invention, the anode active material can reduce the β ^ column and reduce the volume change caused by the reaction of the active material with lithium. The method of preparing the anode active material will be described in detail to prevent the ruthenium and the active material from being mechanically destroyed, thereby achieving high capacitance and an improved charge/discharge cycle. A composite containing ultrafine cerium particles and an oxide surrounding the ultrafine cerium particles by using cerium oxide and an oxide having an erbium (ΔHf0r) having an absolute value greater than the cerium oxide and a negative The type of oxide-forming ruthenium material is mixed together' while being prepared by a mechanochemical method or by subjecting it to a thermochemical reaction to reduce ruthenium dioxide. The ceria material may be Si〇2, si〇, sizcKSiiSia3,
MnSi〇3、FeSi〇3、Li2TiSi03、ZnSi〇3、LiSiON)，其中 Z 可以是Sn、Mn、Fe、Li、Zn、或Ti，或是可使用機械活 化的二氧化矽。機械活化的二氧化矽代表一種具有超細顆 粒體積的氧化物。可藉由一球磨製程來提供該機械活化的 氧化物。具有一超細顆粒體積的該機械活化的氧化物表現 出諸如較高的機械強度、較高的表面積及改良的反應性等 效應。因此，使用該機械活化的氧化物可降低機械化學及 熱化學反應的反應時間並精細控制該複合物的顆粒大小。 對該具有氧化物形成焓（△ Hf()r)之絕對值大於該二氧 化矽及具有負型氧化物形成焓之材料，可使用能還原該二 氧化矽的金屬元素或内含這些金屬元素的化合物。該金屬 元素的較佳例子包括Al、Fe、Li、Mn、Ni、Co、Sn、V、 In、Cr、Y、Ge、Ta、Mg、Ca、Mo、Sb、Ti、Zr、Nb、P、 B、Li3N 等。 1287890 該機械化學製程可包括例如，高能球磨（high energy ball milling)，且如下述，在此製程中發生一合金化反應。 此外，該合金化反應也可藉由熱化學反應來發生。該熱化 學反應係藉由熱處理反應物以誘發該合金化反應。該熱處 理合金化反應較佳係在惰性環境下（例如，氬氣）於1 5 0 °C 至1 500°C的溫度下熱處理反應物，接著再施以電爐冷卻或 綷熄。MnSi〇3, FeSi〇3, Li2TiSi03, ZnSi〇3, LiSiON), wherein Z may be Sn, Mn, Fe, Li, Zn, or Ti, or mechanically activated cerium oxide may be used. Mechanically activated ceria represents an oxide having an ultrafine particle volume. The mechanically activated oxide can be provided by a ball milling process. The mechanically activated oxide having an ultrafine particle volume exhibits effects such as higher mechanical strength, higher surface area, and improved reactivity. Thus, the use of the mechanically activated oxide reduces the reaction time of the mechanochemical and thermochemical reactions and finely controls the particle size of the composite. For the material having the oxide forming enthalpy (ΔHf()r) having an absolute value larger than the cerium oxide and having a negative-type oxide forming cerium, a metal element capable of reducing the cerium oxide or containing the metal element may be used. compound of. Preferred examples of the metal element include Al, Fe, Li, Mn, Ni, Co, Sn, V, In, Cr, Y, Ge, Ta, Mg, Ca, Mo, Sb, Ti, Zr, Nb, P, B, Li3N, etc. 1287890 The mechanochemical process can include, for example, high energy ball milling, and as described below, an alloying reaction occurs during the process. Furthermore, the alloying reaction can also take place by a thermochemical reaction. The thermal chemical reaction induces the alloying reaction by heat treating the reactants. The heat treatment alloying reaction is preferably carried out by heat-treating the reactants under an inert atmosphere (e.g., argon) at a temperature of from 150 ° C to 1,500 ° C, followed by electric furnace cooling or quenching.
SiOx+My—Si+MyOx 矽氧化物（S i Ο x)係以Μ還原成元素石夕，因此所得的 MyOx氧化物係作為一環繞矽的母相。當該矽相與鋰反應 時，爲改善母相受體積變化的影響及減輕拉力效應，鋰離 子穿過母相的傳導特性等限制，可在母相中添加諸如 U2〇、Li202、LiN03及Li2S等鋰化合物與Μ —起進行機 械合金化反應。這些鋰化合物係分散在母相的氧化物中或 與氧化物發生化學鍵結以形成一錯化氧化物。因此，可獲 得一具有超細矽相分散在母相氧化物中的複合物。SiOx+My-Si+MyOx yttrium oxide (S i Ο x) is reduced to lanthanum by lanthanum, so the obtained MyOx oxide acts as a mother phase of a surrounding ruthenium. When the ruthenium phase reacts with lithium, in order to improve the influence of the volume change of the mother phase and to reduce the tensile effect, the conduction characteristics of lithium ions passing through the parent phase, etc., U2〇, Li202, LiN03, and Li2S may be added to the mother phase. The lithium compound is mechanically alloyed with ruthenium. These lithium compounds are dispersed in the oxide of the parent phase or chemically bonded to the oxide to form a disordered oxide. Therefore, a composite having an ultrafine 矽 phase dispersed in the parent phase oxide can be obtained.
相對於1莫耳該石夕氧化物來說，Μ的用量較佳是約〇 3 至4莫耳。當Μ的用量低於〇·3莫耳時，該矽氧化物會保 持與奈米矽分開的狀態，則在第一次充電/放電時，該不可 逆電容將明顯變高。當Μ的用量超過4莫耳時，過多的Μ 會造成體積膨脹，因而破壞該充電/放電的週期特性。相對 於1莫耳該矽氧化物來說，鋰化合物的用量較佳是在〇到 0.6莫耳間。 所獲得之該内含妙相氧化物的複合物可直接作為陽極 7 1287890 活性材 種1¾極 的複合 碳 括教碳 包括， 外，爲 過的結 此表面 象。對 晶度或 碳化該 乾式及 來進行 料，或是該複合物可與碳材料混合後再一起作為一 ’舌性材料。與碳材料混合可提供該内含矽相氧化物 物較高的導電性並増強減輕拉力效應。 材料可包括非晶型碳或結晶碳。非晶型碳的例子包 (低溫硬化碳）或硬碳（高溫硬化碳）。結晶碳的例子 例如，板狀、球形或纖維形的天然或人工石墨。此 改善鋰二次電池的低溫特性，較佳係使用表面處理 曰厌（石墨）即使疋使用丙稀碳酸g旨作為電解質， 處理過的結晶碳在吸留鋰時也不會表現出脫層現 表面處理該結晶碳的方法來說，可使用涉及以低結 非晶型的碳先質塗覆該結晶碳，之後施以熱處理以 碳先質的方法來進行表面處理。此塗覆方法可包括 濕式混合。此外，也可使用一諸如化學氣相沉積法 〇 車父佳疋，該内含矽相氧化物的複合物及碳材料係以 5-90 : 95-1 0的重量比例混合。當該内含矽相氧化物的複 合物的比例低於5 % (重量％)時，其不會對電池電容有明顯 貝獻。相反的，如果其重量比超過9 〇 %時，則因與體積膨 脹的相關問題而造成充電/放電循環週期特性被破壞。 該内含石夕相氧化物的複合物及碳材料可以一種混合物 形式使用或此混合物可被加以球磨以誘發其間的化學鍵 結，以獲得一均一的複合物。但是，因球磨造成碳材料表 面積增加，因此使不可逆電容量提高。，特定言之，當以石 墨作為該碳材料時，該不可逆電容量會明顯降低。以一低 1287890 結晶度或非晶型碳塗覆該内含奈米矽相氧化物複合物_ 材料，以改良其表面時，則可明顯降低該不可逆電容量 因此可改善該充電/放電循環週期特性。 改良該内含奈米砍相氧化物複合物_碳材料表面的 法，可使用涉及以低結晶度或非晶型碳先質來塗覆該内 奈米石夕相氧化物複合物-碳材料，並加熱處理以碳化該碳 質的方法。此塗覆方法可包括乾式及濕式混合。此:， 可使用一諸如化學氣相沉積法來進行。 實施例 以下，將藉由實施例詳細說明。但是，該等實施例係 闡述本發明内容之用，本發明範疇並不僅限於所揭示實 例。 實施例1 以1 · 1 · 0.2的比例混合Si0、A1與Li2〇2，並球磨 藉由機械化合金反應製備出環繞奈米矽的A1_Li-0氧化物 此内含矽氧化物的複合物與碳（SFG 44，石墨）以50: 50的 例混合，之後球磨以製備出一内含奈米矽氧化物複合物_石 的陽極活〖生材料。第丨圖示出該活性材料的X光繞射圖案 一球磨時間（5、1 〇及30分鐘）之間的關係。隨著球磨時間 加，石墨結構也出現變化，但該内含奈米矽的複合物則 此變化。此外，當以Scherrer方程式及χ光繞射圖案來計 矽結晶顆粒大小時，發現該矽具有16 2奈米之奈米結晶 構0 碳 方 含 先 也 供 施 以 〇 比 墨 與 增 無 算 結 1287890 該内含奈米矽氧化物複合物-石墨之活性材料（球磨1 0 刀鈿）的充電/放電電容曲線與充電/放電循環週期間的關係 示於第2圖。在第2圖中，□代表放電電容且。代表充電電 容。如第2圖所示，所製備的陽極活性材料表現出一約為6〇〇 mAh/g的高電容和極佳的充電/放電特性。 膏施例2 為了以低結晶碳材料進行塗覆，將實施例丨所製備之該 内含奈米矽氧化物複合物-石墨之活性材料（球磨ι〇分鐘）與 一碳先質（煤焦）混合，之後在碳化過程藉由一熔化過程將該 碳先質碳化’之後在氬氣及刚。c的溫度下熱處理！小時。 所得之陽極活性材料的充電/放電f容與充電/放電週期的關 係示於第3圖。第3圖示出該陽極活性材料具有一約為42〇 mAh/g的電容，其係遠高於石墨的理論電容（372 和極佳的充電/放電特性。此外，如第3圖所示，相較於實 施例1中表面不曾塗覆低結晶度碳材料的陽極材料而言，此 陽極材料之初始不可逆電容係明顯降低。 因此，在表面塗覆低結晶度碳材料不僅可降低初始不可 逆電容，還可明顯改善該充電/放電週期特性。 實施例3 為了以低結晶碳材料進行塗覆，將實施例丨所製備之該 内含奈米矽氧化物複合物-石墨之活性材料（球磨5分鐘）與一 碳先質（煤焦）混合，之後在氬氣及90(rc的溫度下熱處理i 10 1287890 小時。所獲彳于該陽極材料的x光繞射圖案與其充電/放電週 期的關係示於第4圖。可從第4圖上降低的石墨尖峰值確認 該複合物表面確實塗覆了一低結晶度的碳材料層。僅管熱處 理a度為9〇〇 c ’該石夕或鋁（三氧化二鋁）的尖峰並未大幅升 高，且其存在於該奈米結晶狀態中。當以Scherrer方程式及 X光繞射圖案來計算矽結晶顆粒大小時，發現該矽具有丨4 8 奈米之奈米結晶結構。此結果與實施例1未經熱處理的X光 繞射圖案結果類似。亦即，在以機械化學製程製備而成的實 施例1的陽極活性材料的情況下，由於矽係以奈米顆粒方式 存在，或其中有一陣列，因此即使加熱溫度為90(rc，仍可 維持其中的奈米結晶狀態。 第5圖示出實施例3之％極材料的充電/放電電容與充電 /放電週期的關係。如第5圖所示，該陽極活性材料具有一約 為465 mAh/g的電容和極佳的充電/放電特性及一低的初始 不可逆電容。 第ό圖示出以個別充電/放電週期將實施例3的陽極材料 充電後，再經10分鐘休息時間之後，其之開放電路電位。 如第6圖所示，該開放電路電位（〇cv)在重複充電/放電週期 後幾乎維持不變。但是，在充電/放電時，因為矽與鋰反應導 致體積變化，而造成矽出現裂痕。此外，矽活性顆粒也遭到 破壞，導致内電阻增加。因此，該開放電路電位會隨著充電 /放電週期而增加。因此，開放電路電位沒有變化代表該塗覆 了碳的奈米矽-碳複合物可防止矽因與鋰反應致使體積變化 而出現龜裂的情況，此情況係之前的矽材料最主要的缺點。 11 1287890 這些實施例的結果將參照實施例4詳細說明。 實施例4 以3 ·· 4.2 : 〇·3的比例混合SiO、A1與Li2S，並球磨以 藉由機械化合金反應製備出環繞奈米矽的Al-Li-〇-S氧化 物。第7及8圖分別顯示該内含石夕氧化物的複合物相對於充 電/放電週期時的充電/放電電容與開放電路電位（〇cv)。如第 7及8圖所示，充電/放電電容係隨著充電/放電週期（線心的 增加而下降，同時OCV也隨之下降到一低電位（線a)，與該 充電/放電曲線類似。此代表在充電/放電時，由於與鐘之間 的反應導致體積變化進而使Si龜裂，且矽活性材料顆粒被破 壞，因此充電/放電電容下降且内電阻增加。 但疋’右1%極材料係藉由混合該内含石夕氧化物的複合物 與碳（SFG44,石墨）的方式製備而成，如第7及8圖所示，則 其充電/放電電容（線b)與0CV(線b)曲線可分別保持值定。 第9圖顯示一電極之内含矽氧化物複合物-碳活性材料 經過40次充電/放電後的SEM圖。如第9圖所示，該内含石夕 氧化物複合物碳1¾'極材料龜裂的程度相當低。 f施例5 以1 : 1 : 0·2的比例混合SiO、Ai與Li2〇2，並球磨以 猎由機械化合金反應製備出環繞奈米碎的Al-Li-Ο氧化物。 此内含梦乳化物的複合物與碳（SFG 6，石黑）以50: 50的比 例混合，之後球磨以製備出一内含奈米矽氧化物複合物-石墨 12 1287890 的陽極活性材料。將此複合物與一碳先質（煤焦）混合並在氬 乳及900 C溫度下熱處理！小時，以獲得該陽極材料。第μ 圖顯不所獲陽極材料相對於充電/放電週期的放電電容。如第 ίο圖所不，該陽極材料具有一約53〇 mAh/g的電容，及一 極佳的的充電/放電特性。此代表即使添加具有不同形狀及 顆粒大小的碳也可提供極佳的特性。 實施例6 务以1 : 1 : 〇·2的比例混合SiO、A1與Li2〇2，並球磨以 藉由機械化合金反應製備出環繞奈米矽的A1-U-〇氧化物。 此内含矽氧化物的複合物與碳（SFG 6 ,石墨）以60 : 4〇的比 例=口，之後球磨以製備出一内含奈米矽氧化物複合物-石墨 的陽，活性材料。將此陽極活性材料與一碳先質（煤焦）混合 並在氬氣及9GG C溫度下熱處理1小時，以獲得該陽極材料。 第11圖顯不所獲陽極材料相對於充電/放電週期的放電電 容。如第11圖所示，該充電/放電曲線係在一低電位下出現， 且其適合作為一鋰二次電池的陽極材料。 φ 第1 2圖顯示上述陽極材料相對於充電/放電週期之充電 放電電奋。如第1丨圖所示，該陽極材料具有一約55〇 mAh/g 的電谷’及一極佳的的充電/放電特性。 第U圖顯示環繞奈米矽的A1-L“〇氧化物陣列的χ光 繞射圖案’其係藉由機械化合金反應以丨：〇 67 : 〇 2的比例 13 1287890 混合SiO、A1與Li2〇2，與一藉由機械化合金反應所製備出 的一内含奈米矽氧化物複合物（將粉末狀si〇、八丨與Li2〇2混 合並在虱氣、5001：下加熱5小時所製備而成的）的方式所製 備而成的。由此藉由機械化合金反應與熱化學反應所製備而 成的該内含奈米矽的複合物，表現出類似的X光繞射圖 案，因此可看出熱化學反應也可輕易的獲得奈米等級的含矽 氧化物複合物。 產業利用性 依據本發明的陽極活性材料可藉由限制並減輕因與鐘 反應所致之體積變化來防止該陽極活性材料被機械性破 壞’進而實現高電容及一改良的充電/放電週期。 習知技藝亡士從上述說明中可輕易了解本發明特徵，在 不悖離本發明範轉下，盤太 了對本發明作不同程度的變化或修 改，以達本發明所揭示的相同 ^ ^ 邊寺變化或修改仍應视 為本發明附隨申請專利範圍所定義的範疇。 【圖示簡單說明】 二複…碳的一， 第圖示出！^含奈米石夕氧化物複 分鐘）的混合物，相對# "與石墨（球磨10 第于出h ㈣期之充電/放電電容。 第圖亦出貫施例2的陽極材料相對 之充電/放電電容。 、；无電/放電週期 14 1287890 材料的X光繞射圖案。 材料相對於充電/放電週期 第4圖示出實施例3之陽極 第5圖示出實施例3的陽極 之充電/放電電容。 <叮杜无電後經過分 的休息後，其開放電路電位（〇Cv)；te姐、X y (UCV)相對於充電/放電週期的 係0 内ό矽氧化物複合物相對於充電 〇 内含矽氧化物複合物的開放電路The amount of cerium is preferably from about 3 to 4 moles relative to 1 mole of the cerium oxide. When the amount of ruthenium is less than 〇·3 moles, the ruthenium oxide will remain in a state separate from the nano 矽, and the irreversible capacitance will become significantly higher at the first charge/discharge. When the amount of cerium exceeds 4 moles, excessive enthalpy causes volume expansion, thereby damaging the periodic characteristics of the charging/discharging. The lithium compound is preferably used in an amount of from 0.6 to 2 moles per mole of the cerium oxide. The obtained composite containing the wonderful phase oxide can be directly used as an anode 7 1287890 active material species 13⁄4 pole composite carbon engraved carbon includes, in addition, the surface of the surface. The dry and finished materials are crystallized or carbonized, or the composite may be mixed with a carbon material to serve as a ' tongue material. Mixing with the carbon material provides higher conductivity of the contained cerium phase oxide and lessens the tensile effect. The material may include amorphous carbon or crystalline carbon. Examples of amorphous carbon (low-temperature hardening carbon) or hard carbon (high-temperature hardening carbon). Examples of the crystalline carbon are, for example, plate-shaped, spherical or fibrous natural or artificial graphite. This improves the low-temperature characteristics of the lithium secondary battery, and preferably uses a surface treatment anodic (graphite). Even if propylene carbonate is used as the electrolyte, the treated crystalline carbon does not exhibit delamination when occluding lithium. In the method of surface-treating the crystalline carbon, the surface treatment may be carried out by coating the crystalline carbon with a carbonaceous precursor of a low-junction amorphous type, followed by heat treatment with a carbon precursor. This coating method can include wet mixing. Further, a chemical vapor deposition method such as a composite of a cerium phase oxide and a carbon material may be used in a weight ratio of 5-90: 95-1 0. When the proportion of the complex containing the cerium phase oxide is less than 5% by weight, it does not significantly contribute to the battery capacity. On the contrary, if the weight ratio exceeds 9 〇%, the charge/discharge cycle characteristics are deteriorated due to problems associated with volume expansion. The composite containing the stone phase oxide and the carbon material may be used in the form of a mixture or the mixture may be ball milled to induce chemical bonding therebetween to obtain a uniform composite. However, since the surface area of the carbon material is increased by the ball milling, the irreversible capacity is increased. In particular, when graphite is used as the carbon material, the irreversible capacity is significantly reduced. Coating the inner nano-ply phase oxide composite material with a low crystal temperature of 1287890 or amorphous carbon to improve the surface thereof can significantly reduce the irreversible capacity and thus improve the charge/discharge cycle characteristic. The method for improving the surface of the nano-phase-cut oxide compound-carbon material can be used to coat the endo-star phase oxide composite-carbon material with low crystallinity or amorphous carbon precursor. And heat treatment to carbonize the carbonaceous material. This coating method can include dry and wet mixing. This: It can be carried out using a method such as chemical vapor deposition. EXAMPLES Hereinafter, the examples will be described in detail. However, the examples are intended to be illustrative of the present invention and the scope of the invention is not limited to the disclosed embodiments. Example 1 Si0, A1 and Li2〇2 were mixed at a ratio of 1 · 1 · 0.2, and ball-milling was carried out by mechanized alloying to prepare an A1_Li-0 oxide surrounding the nano-ruthenium. (SFG 44, graphite) was mixed in an example of 50:50, followed by ball milling to prepare an anode active material containing a nano-indium oxide composite-stone. The figure shows the relationship between the X-ray diffraction pattern of the active material and the ball milling time (5, 1 〇 and 30 minutes). As the ball milling time increases, the graphite structure also changes, but the composition containing the nano bismuth changes. In addition, when the crystal particle size is calculated by the Scherrer equation and the diffractive diffraction pattern, it is found that the crucible has a crystal structure of 16 2 nm, and the carbon is contained first, and is also applied to the indole ink and the addition of no knot 1287890. The relationship between the charge/discharge capacitance curve of the nano-indium oxide composite-graphite active material (ball milled 10 knives) and the charge/discharge cycle is shown in Fig. 2. In Fig. 2, □ represents the discharge capacitance and. Represents the charging capacitor. As shown in Fig. 2, the prepared anode active material exhibited a high capacitance of about 6 mAh/g and excellent charge/discharge characteristics. Paste Example 2 In order to coat with a low crystalline carbon material, the intrinsic nano-indium oxide composite-graphite active material prepared in Example ( (ball mill) and a carbon precursor (coal) Mixing, then carbonizing the carbon precursor during a carbonization process by a melting process followed by argon and just. Heat treatment at the temperature of c! hour. The relationship between the charge/discharge f capacity of the obtained anode active material and the charge/discharge cycle is shown in Fig. 3. Figure 3 shows that the anode active material has a capacitance of about 42 mAh/g which is much higher than the theoretical capacitance of graphite (372 and excellent charge/discharge characteristics. Further, as shown in Fig. 3, Compared with the anode material in which the surface of the embodiment 1 has not been coated with a low crystallinity carbon material, the initial irreversible capacitance of the anode material is significantly reduced. Therefore, coating the surface with a low crystallinity carbon material can not only reduce the initial irreversible capacitance. The charging/discharging cycle characteristics can also be remarkably improved. Example 3 In order to coat with a low crystalline carbon material, the intrinsic nano-indium oxide composite-graphite active material prepared in Example ( (ball mill 5) Minutes) mixed with a carbon precursor (coal), then heat treated at argon and 90 (rc temperature i 10 1287890 hours. The relationship between the x-ray diffraction pattern obtained from the anode material and its charge/discharge cycle It is shown in Fig. 4. It can be confirmed from the reduced graphite peak value on Fig. 4 that the surface of the composite is indeed coated with a layer of carbon material having a low crystallinity. Only the heat treatment a degree is 9〇〇c '. Aluminum (aluminum oxide) The peak does not increase significantly, and it exists in the crystal state of the nano. When the size of the ruthenium crystal is calculated by the Scherrer equation and the X-ray diffraction pattern, it is found that the ruthenium has a nanocrystal of 丨48 nm. The results are similar to the results of the X-ray diffraction pattern of Example 1 which has not been heat treated. That is, in the case of the anode active material of Example 1 prepared by a mechanochemical process, since the lanthanide is a nanoparticle. The mode exists, or has an array therein, so even if the heating temperature is 90 (rc, the crystal state of the nanocrystal can be maintained therein. Fig. 5 shows the charge/discharge capacitance and the charge/discharge cycle of the % pole material of Example 3. Relationship. As shown in Fig. 5, the anode active material has a capacitance of about 465 mAh/g and excellent charge/discharge characteristics and a low initial irreversible capacitance. The figure shows the individual charge/discharge cycles. After charging the anode material of Example 3, after a rest period of 10 minutes, the circuit potential was opened. As shown in Fig. 6, the open circuit potential (〇cv) was almost maintained after repeated charge/discharge cycles. However, during charging/discharging, the volume of the crucible reacts with lithium, causing cracks in the crucible. In addition, the active particles of the crucible are also destroyed, resulting in an increase in internal resistance. Therefore, the open circuit potential is charged. / The discharge cycle is increased. Therefore, the change in the open circuit potential means that the carbon-coated nano-ruthenium-carbon composite prevents cracking due to volume change caused by the reaction with lithium, which is the former enthalpy. The most important disadvantages of the material. 11 1287890 The results of these examples will be explained in detail with reference to Example 4. Example 4 SiO, A1 and Li2S are mixed in a ratio of 3 ·· 4.2 : 〇·3 and ball milled to react by mechanized alloy An Al-Li-〇-S oxide surrounding the nano bismuth was prepared. Figures 7 and 8 show the charge/discharge capacitance and the open circuit potential (〇cv) of the composite containing the stellite oxide with respect to the charge/discharge cycle, respectively. As shown in Figures 7 and 8, the charge/discharge capacitance decreases with the charge/discharge cycle (the core increases, and the OCV also drops to a low potential (line a), similar to the charge/discharge curve. This represents that when charging/discharging, the volume change causes the Si to crack due to the reaction with the clock, and the active material particles are destroyed, so the charge/discharge capacitance decreases and the internal resistance increases. The polar material is prepared by mixing the composite containing the stellite oxide with carbon (SFG44, graphite), as shown in Figures 7 and 8, the charge/discharge capacitance (line b) and 0CV. The (line b) curve can be kept constant. Fig. 9 shows an SEM image of the cerium-containing oxide composite-carbon active material in one electrode after 40 times of charging/discharging. As shown in Fig. 9, the inclusion The degree of cracking of the 13⁄4' pole material of the Shixi oxide composite is quite low. f Example 5 Mix SiO, Ai and Li2〇2 in a ratio of 1: 1: 0, and ball mill to prepare by mechanized alloy reaction. A nano-crushed Al-Li-Ο oxide. This complex containing dream emulsion and carbon (SFG 6, Stone black) was mixed in a ratio of 50:50, followed by ball milling to prepare an anode active material containing a nano-n-oxide composite-graphite 12 1287890. The composite was mixed with a carbon precursor (coal) and Heat treatment at argon milk and at a temperature of 900 C for an hour to obtain the anode material. The μ map shows the discharge capacity of the anode material relative to the charge/discharge cycle. As shown in Fig. ί, the anode material has an approx. 53 mAh / g of capacitance, and an excellent charge / discharge characteristics. This means that even the addition of carbon with different shapes and particle sizes can provide excellent characteristics. Example 6 1: 1 : 〇 The ratio of 2 is mixed with SiO, A1 and Li2〇2, and ball-milled to prepare an A1-U-〇 oxide surrounding the nano-bismuth by mechanized alloy reaction. The complex containing cerium oxide and carbon (SFG 6 , Graphite) is prepared at a ratio of 60:4 = = port, followed by ball milling to prepare a positive active material containing a nano cerium oxide composite-graphite. This anode active material is mixed with a carbon precursor (coal). And heat treatment at argon and 9GG C for 1 hour to obtain The anode material. Figure 11 shows the discharge capacitance of the anode material relative to the charge/discharge cycle. As shown in Fig. 11, the charge/discharge curve appears at a low potential, and it is suitable as a lithium two The anode material of the secondary battery. φ Figure 12 shows the charging and discharging of the above anode material with respect to the charge/discharge cycle. As shown in Fig. 1, the anode material has an electric valley of about 55 mAh/g. And an excellent charge/discharge characteristic. Figure U shows the A1-L "coil diffraction pattern of the tantalum oxide array" surrounding the nano-ruthenium by mechanically alloying reaction: 〇67 : 〇2 The ratio 13 1287890 is mixed with SiO, A1 and Li2〇2, and a nano-indium-containing oxide composite prepared by reacting a mechanized alloy (mixing powdered si〇, gossip and Li2〇2 and Prepared by the method of helium, 5001: prepared by heating for 5 hours. Thus, the nano-indium-containing composite prepared by mechanized alloy reaction and thermochemical reaction exhibits a similar X-ray diffraction pattern, so that it can be seen that the thermochemical reaction can also easily obtain nanometer. Grades of cerium-containing oxide complexes. Industrial Applicability The anode active material according to the present invention can prevent the anode active material from being mechanically broken by limiting and reducing the volume change due to the reaction with the clock, thereby achieving high capacitance and an improved charge/discharge cycle. A person skilled in the art can easily understand the features of the present invention from the above description. Without departing from the scope of the invention, the disk may be changed or modified to varying degrees to the present invention to achieve the same degree as disclosed in the present invention. Temple variations or modifications are still considered to be within the scope of the invention as defined by the scope of the patent application. [Simple illustration] Two complexes... One carbon, the first picture shows! ^ Mixture containing nanometer sulphur oxides, relative to # " and graphite (ball mill 10 first in the h (four) period of charge / discharge capacitance. The figure also shows the anode material of Example 2 relative to the charge / Discharge Capacitance; No Charge/Discharge Cycle 14 1287890 X-ray diffraction pattern of material. Material shows the anode of Example 3 with respect to the charge/discharge cycle. Figure 5 shows the charge of the anode of Example 3 / Discharge capacitance. <After the rest of the cycle, the open circuit potential (〇Cv); te sister, X y (UCV) relative to the charge/discharge cycle of the system 0 ό矽 oxide complex relative Open circuit containing cerium oxide complex in charging crucible
第7圖示出實施例4的 /放電週期之充電/放電電容 第8圖示出實施例4的 電位（OCV)。 第9圖示出實施例4的内含矽氧 ▽乳化物複合物-碳陽極材 料經過40次充電/放電後其SEM照片。 第1 0圖示出實施例5的陽極材斜鈿斟认云+ , 何针相對於无電/放電週期 之放電電容。 第11圖示出實施例6之陽極材料的充電/放電曲線。Fig. 7 shows the charge/discharge capacitance of / discharge period of the fourth embodiment. Fig. 8 shows the potential (OCV) of the fourth embodiment. Fig. 9 is a SEM photograph of the indole oxime emulsifier composite-carbon anode material of Example 4 after 40 times of charging/discharging. Fig. 10 shows the anode material of Example 5, which is a discharge capacitor with respect to the period of no electric/discharge period. Fig. 11 is a graph showing the charge/discharge curve of the anode material of Example 6.
第1 2圖示出實施例6之陽極材料相對於充電/放電週期 之放電電容。 第1 3圖顯示實施例7之陽極材料中該内含矽氧化物複 合物的X光繞射圖案。 15Fig. 12 shows the discharge capacity of the anode material of Example 6 with respect to the charge/discharge cycle. Fig. 13 shows an X-ray diffraction pattern of the cerium-containing oxide composite in the anode material of Example 7. 15