1332277 九、發明說明： 發明所屬之技術領域 本發明係關於一種用於鋰離子-兮 丁一-人電池的負極活性材 料’尤其有關一種以石夕作真拿i 士 下马主要成份的負極活性材料。 先前技術 工作低壓與優異的 之負極活性材料。 ，約 370 mAh/g(或BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative active material for a lithium ion-tin-man battery, and more particularly to an anode active material which is mainly used as a main component of Shi Xiazhen. . Prior art works with low pressure and excellent negative active materials. , about 370 mAh/g (or
石墨因為具有成本低、·低及平坦的 可逆性而為商業化鋰離子二次電池常用 然而’石墨具有相對為低的理論電容值 830 Ah/L)的缺點。 在尋找更高電容的負極活性材料的過程中，很多努力 係集中在以梦為基礎的材料上。作為_子二次電池的負 極活性材料，矽具有一大於3〇〇〇 mAh/g的理論電容值。但 是，碎在充/放電循環十會產生很大的體積變化（大於 3〇〇%)，以及矽具有差的電子傳導性，使得其在應用上被受 限。已知具有石夕薄膜塗層的負極，其係藉由真空蒸鍍被形 成，可以在超過3000 mAh/g電容下被充/放電3〇〇循環， 其中包括修飾該薄膜的微結構及薄膜與基材的界面、或使 用含非晶矽的合金的薄膜。然而至目前為止仍然沒有一種 技術可以成功的將矽運用作為傳統鋰離子二次電池之厚膜 粒子電極構形，最主要的原因就是以上所提及之矽在充/放 電循環的大體積變化。 發明内容 5 本發明的一主要目的在於提供-種新穎的以石夕為基礎 的鋰離子二次電池的負極活性材料。 X月的另目的在於提供一種新穎的以矽為基礎的 鋰離子二次電池的負極活性材料的製備方法。 本發明的又一目的古认坦 的在於k供一種鋰離子二次電池，其 具有以矽為基礎的負極活性材料。 為了達成上述發明目的，本發明揭示了一種多孔的複 合物粒子作為該負極活性材料。該複合物主要由碎及金屬 夕化物、·且《孩夕孔的杻子具有i 〇·6〇體積％百分比的内孔 隙度（imra-particle por〇sityR 1〇·5〇〇〇 奈米的粒子内孔 洞。在充放電鋰離子礙入/欲出的循環中，本發明的多孔的 複合物粒子相較於使用㈣粒子所製備的負極，顯現出明 顯較低的厚度膨脹率及電容量衰退率。此等改良主要歸因 於本發明的複合物粒子之預置的内孔洞部份容納了㈣合 金化所產生的體積膨脹。 實施方式 本發明揭示一種用於鋰離子二次電池的負極活性材 料，包含多孔的粒子，該多孔的粒子為更小的si 一次粒子 與金屬石夕化物的一次粒子連結而成之複合物二次粒子，且 該多孔的粒子具有1〇〜60體積％之内孔隙度及孔徑為 10〜5000奈米的内孔洞，以約200奈米為較佳。 若該多孔粒子之内孔隙度小於10%，則將無法達到顯 著之電極穩定效果。若大於60%，則粒子之體積比電容量 1332277 太低’而降低經濟利用價值。 較佳的’該多孔的粒子具有30〜60%的内孔隙度及 〇·1〜100微米的粒徑’及該金屬係選自鎳、鐵、銅、鈷、鎢、 鈦之一或其組合。 較佳的，該多孔的粒子為矽與矽化鎳（NiSi)的複合物。 較佳的，該多孔粒子’包含矽與金屬矽化物的莫耳比為 1:0.5至1:1〇。若金屬矽化物的含量低於莫爾比=1:〇 5含 量’則將無法達到滿意之電極穩定效果。若金屬矽化物的 3里兩於莫爾比= ι:ι〇含量’則複合物粒子之電容量太 低’而無經濟利用價值。Si與金屬矽化物的莫耳比，以 1·1〜1:2為更佳。 較佳的，組成該複合物的矽與金屬矽化物的一次粒子 粒徑不大於5微米，以不大於2微米更佳。當一次粒子的 粒徑愈小表示它們的分佈愈均勻。 較佳的’§亥複合物的多孔粒子之内孔隙度約4 〇〜5 〇體 積 0/〇。 一種適合製備本發明的負極活性材料的方法，包含將 石夕粒子反應物與金屬粒子反應物於一惰性氣氛下一起研 磨，以形成金屬矽化物：將研磨所得到的產物浸於一酸中， 使未反應的金屬溶解於該酸性溶液中；通過固液分離的手 段得到多孔的複合物粒子；清洗該多孔的複合物粒子上的 殘留酸及乾燥清洗過的多孔的複合物粒子。 較佳的’該矽粒子反應物具有0H〇〇微米的粒徑， 及該金屬粒子反應物具有〇_1〜1〇〇微米的粒徑。更佳的， 7 1332277 該矽粒子反應物的粒徑約等於該金屬粒子反應物的粒徑。 較佳的，該金屬矽化物及矽粒子反應物實質上不溶於 該酸。 本發明亦揭示一種鋰離子二次電池，包含一正極；一 負極，一隔離膜其隔開該正極及負極；及一電解質其形成 該正極與負極之間的—鋰離子通道，其中該負極包含一集 電流（current collector)基材；及附著在該基材的表面上的 一負極活性材料；其特徵包含該負極活性材料包含多孔的 粒子，及該多孔的粒子為更小的矽一次粒子與金屬矽化物 的一次粒子連結而成之複合物二次粒子，且該多孔的粒子 具有10〜60體積％之内孔隙度，及孔洞孔徑為1〇〜5〇〇〇奈 米的内孔洞。 較佳的’該多孔的粒子具有30〜60體積％的内孔隙度 及0.1〜100微米的粒徑’及其中該金屬係選自鎳、鐵、銅、 鈷、鎢、鈦之一或其組合。 較佳的’該多孔的粒子為矽與矽化鎳的複合物。 較佳的’該複合物的妙與金屬石夕化物的莫耳比為1:〇.5 至1:10，以約1:1〜1:2為更佳的。 較佳的’組成該複合物的矽與金屬矽化物的一次粒子 之粒徑不大於5微米，以不大於2微米更佳。 較佳的，該複合物的内孔隙度約30〜60體積％，以40〜50 體積％為更佳者。 較佳的，該多孔的粒子具有的内孔洞的孔徑約2〇〇奈 米0 8 1332277 實施例： 將高純度的元素態粉末矽（99%，-325網目，Aldrich 公司）和鎳（5 μιη，CERAC公司）加予機械式合金化而合成出 合金粉末，其中矽及鎳的用量莫爾比分別為1:2。機械式合 金化使用一行星球磨機（planetary mill) (Fritsch公司，型號 Pulverisette P7)及不銹鋼製球磨罐和球於氬（Ar)氣氛下進 行’其中球和粉末的重量比為14 : 1，以及〇.5重量。/。的硬 脂酸[CH3(CH2)16COOH]被作為潤滑劑加入。在以400 rpm 磨粉16小時後，一中間產物含有鎳、矽、與矽化鎳之複合 材料被形成。將磨粉獲得的產品置於〇.5 ]y[硝酸水溶液1 小時以侵钱掉鎳《溶於該硝酸水溶液中的鎳量以電感耦式 電漿（inductively coupled plasma，ICP)頻譜儀（spectroscopy) (Optima公司，型號3000XL)加予測量。最後從該硝酸水溶 液中分離出粉末，以水清洗及於真空爐中以5〇。〇乾燥6小 時’於是得到矽與矽化鎳連結之複合物二次粒子。 負極塗佈組合物由62重量％的上述製備的矽與矽化鎳 複合物粒子’ 3 0重量％的導電性添加物及8重量％的黏結 劑（binder)所組成，其中該重量百分比係以組合物的乾重為 基礎。該黏結劑係本乙稀-丁二燦橡膠（styrene_butadiene rubber，SBR)(Asahi Chemicals 公司，代號 L1571)和鈉-羰基 -曱基纖維素（sodium-carboxyl-methylcellulose, SCMC) (DKS International 公司，代號 WS-C，Collogen)以 1 : 1 重 量比所組成。該導電性添加物係由石墨片（graphite 9 1332277 (TIMCAL公司’代號KS6)和奈米碳黑（timcal公司代 號SUPerP，40奈米）以5: 1重量比所組成。該負極塗佈组 &物和去離子水以重χ Λ i :2混合而得到_漿狀物。將此 聚狀物塗佈於-㈣的兩表面上，锻壓及乾燥溶劑後獲得 總厚度為64微米的負&，其中銅箔厚度為14微米。 CR2032鈕扣型電池被組裝以進行電化學特性分析。負 極分別使用上述製備之負極和以㈣方法但以㈣取代石夕 與石夕化錄複合物所製備者。正極為鋰落。電解質為溶於乙 稀碳酸醋（ethylene carb〇nate, Ε〇和甲基乙基碳酸酉旨 (methyl ethyl carb〇nate，MEC)體積比 J : 2 的混合液中的 1.0 M LiPFy以下所指之電壓除非特別指日月否則是相對於 該Li正極。 充/放電測試係採用定電流定電壓（CC-CV)模式在電壓 範圍〇·_至UVt間進行。該定電流過程使用〇1 mA/mg的定電流；該定電壓過程使用〇謝v的定電壓和 一截止電流〇·03 A/g。X光繞射儀係使用Mac-Science/MXp 繞射儀及CuKa輕射進行。粒徑測量係藉由光散射分析進 行。孔隙度和孔大小分佈係使用水銀孔徑儀進行。 矽粉末的平均粒徑約20微米，粒徑介於1〇到4〇微米 的粉體佔約77% (體積比)。混合粉末經過16小時球磨後再 以稀硝酸溶液去侵蝕溶解未合金化的鎳，此侵蝕程序的目 的係增加粉末整體的孔隙度。圖一顯示出樣品在經過侵蝕 程序前後的X光繞射圖譜，最終產物只剩矽化鎳（Nisi) 與石夕。考慮錄被溶解量，經計算得硬化錦與妙的重量比約 叫2277 為76/24(莫爾比約i.o/u)。經由侵触程序後的粉末其粒徑 分析結果為-寬廣的粒徑分佈，大於9〇%體積百分比的粉 體其粒徑介於2·Η)微米。如圖二所示，掃描式電子顯微鏡 .與X光能量分析顯示本實驗經由球磨與侵蝕程序所製備的 • 複合物二次粒子為由小於2_0微米矽與矽化鎳一次粒子所 連結組成的一個多孔性架構。圖三為該複合物粒子的孔洞 刀佈之分析結果，此分佈有兩個峰，分別在2〇〇奈米和6〇〇 鲁不米，為一典型的雙峰分佈曲線。對於一個多孔性材料而 S 較大孔洞的峰（600奈米）主要歸因於粒子與粒子間的 $隙所貝獻，其取決於量測時裝填粉體之緊密度，並非粒 •子本身的性質。相反地’較小孔洞的峰(200奈米)則為粒 子内P的孔洞所提供，其尺寸分佈範圍與掃描式電子顯微 鏡所觀察到的結果一致。理論上可以高斯分佈將這兩根峰 •分開計算獲得粒子内部孔洞的全部孔體積，經如此計算為 ’力〇· 151 cc/go考慮矽與矽化鎳的理論密度得此複合物粒子 # 的固體.體積0.238 cc/g， 粒子内孔隙度==(粒子内孔體積）/ (粒子内孔體積+粒干 的固體體積） 可計算出其粒子内孔隙度為38 9%。 純矽電極與本發明製程之含矽與矽化鎳複合物粒子之 .貞極電極的循環壽命測試電容量結果如圖四所示。對於純 石夕負極材料，笛 A ^ β 、& 第一-人充電（鋰遷入）電容量在電流〇 1A/g的 條件下可達到約33⑼mAh/g，但在放電⑽遷出）過程中有 達2/〇的不可逆電容量損失，僅僅經過五次循環次數， 1332277 充電電容量迅速衰退至約200 mAh/g;反觀由複合物粒子 組合之電極在相同的充放電條件下展現出良好的循環穩定 性’第-圈的充電電容量為125G mAh/g，在5G次的^放 電後仍保有540 mAh/g的電容量表現。 面結構進行觀察。樣品的製 在分析前’該循環後的電 對充/放電循環後的電極的剖 備係於氬充氣的手套箱内進行。 極於手套箱内被以二乙基碳酸醋咖邮earb_te，Mc) 潤洗及乾燥。由掃晦顯微鏡觀察觀察發現未經充放電測試 前’純石夕電極與複合物粒子電極的厚度分別為55# Μ微 米、過1 0 -人充放電後，純石夕電極膨服到微米，而複 合物粒子電極僅膨㈣96微米’顯示使用複合物粒子可降 低電極層在充放電時之體積變化，而提高充放電循環的# 定性。 “ 顯而易見地，選用能夠鱼s彳勒士 b巧η in形成合金的金屬，例如，鎳、 銅、鐵、钻、鶴、鈦等今凰，姑丄丄 寻备屬，猎由向能球磨技術與侵蝕程Graphite is commonly used in commercial lithium ion secondary batteries because of its low cost, low and flat reversibility. However, graphite has a relatively low theoretical capacitance value of 830 Ah/L. In the search for higher capacitance anode active materials, much effort has been focused on dream-based materials. As the negative active material of the _ sub-secondary battery, ruthenium has a theoretical capacitance value of more than 3 mA mAh/g. However, the crushing in the charge/discharge cycle produces a large volume change (greater than 3〇〇%), and the flaw has poor electronic conductivity, which makes it limited in application. A negative electrode having a coating of a thin film, which is formed by vacuum evaporation, can be charged/discharged for 3 cycles at a capacitance exceeding 3000 mAh/g, including modifying the microstructure and film of the film. The interface of the substrate or a film using an alloy containing amorphous germanium. However, until now, there is still no technology that can successfully use ruthenium as a thick film particle electrode configuration of a conventional lithium ion secondary battery. The most important reason is the large volume change of the charge/discharge cycle mentioned above. SUMMARY OF THE INVENTION A main object of the present invention is to provide a novel negative electrode active material for a lithium ion secondary battery based on Shixia. Another object of X month is to provide a novel method for preparing a negative active material of a lithium ion secondary battery based on ruthenium. Still another object of the present invention is to provide a lithium ion secondary battery having a negative electrode active material based on ruthenium. In order to achieve the above object, the present invention discloses a porous composite particle as the negative electrode active material. The composite is mainly composed of crushed and metal cerium compounds, and the scorpion of the scorpion has an internal porosity of i 〇·6〇 volume% (imra-particle por〇sityR 1〇·5〇〇〇 nanometer The pores in the particles. In the cycle of charge/discharge lithium ion intrusion/exit, the porous composite particles of the present invention exhibit a significantly lower thickness expansion ratio and capacity decay than the negative electrode prepared using the (iv) particles. The improvement is mainly due to the fact that the pre-defined inner pore portion of the composite particles of the present invention accommodates the volume expansion caused by (iv) alloying. Embodiments The present invention discloses a negative electrode activity for a lithium ion secondary battery. The material comprises porous particles, which are composite secondary particles obtained by joining smaller primary particles of Si and primary particles of metal ceramsite, and the porous particles have a volume of from 1 to 60% by volume. The inner pores having a porosity and a pore diameter of 10 to 5000 nm are preferably about 200 nm. If the porosity of the porous particles is less than 10%, a remarkable electrode stabilizing effect cannot be achieved. If it is greater than 60%, then The volumetric volume of the sub-portion is too low for the capacity 1332277 to reduce the economical use value. Preferably, the porous particles have an internal porosity of 30 to 60% and a particle size of 〇1 to 100 μm and the metal is selected from the group consisting of One or a combination of nickel, iron, copper, cobalt, tungsten, titanium, or a combination thereof. Preferably, the porous particles are a composite of cerium and nickel hydride (NiSi). Preferably, the porous particles comprise strontium and metal bismuth. The molar ratio of the material is 1:0.5 to 1:1. If the metal halide content is lower than the molar ratio = 1: 〇5 content, the satisfactory electrode stabilization effect will not be achieved. If the metal telluride is 3 miles The two molar ratios of Mobbi = ι:ι〇 'the composite particles are too low' and have no economical use value. The molar ratio of Si to metal telluride is preferably from 1·1 to 1:2. Preferably, the primary particles of the ruthenium and the metal ruthenium constituting the composite have a particle diameter of not more than 5 μm and more preferably not more than 2 μm. The smaller the particle diameter of the primary particles, the more uniform their distribution is. The porosity of the porous particles of the §Hai complex is about 4 〇~5 〇Volume 0/〇. A suitable preparation A method of inventing an anode active material comprising: grinding a daylight particle reactant and a metal particle reactant together under an inert atmosphere to form a metal halide: immersing the product obtained by grinding in an acid to make unreacted The metal is dissolved in the acidic solution; the porous composite particles are obtained by means of solid-liquid separation; the residual acid on the porous composite particles is washed and the washed porous composite particles are dried. The reactant has a particle size of 0H 〇〇 micron, and the metal particle reactant has a particle diameter of 〇_1~1 〇〇 micron. More preferably, 7 1332277 the particle size of the ruthenium particle reactant is approximately equal to the reaction of the metal particle. Preferably, the metal halide and cerium particle reactants are substantially insoluble in the acid. The invention also discloses a lithium ion secondary battery comprising a positive electrode; a negative electrode, a separator separating the positive electrode and the negative electrode; and an electrolyte forming a lithium ion channel between the positive electrode and the negative electrode, wherein the negative electrode comprises a current collector substrate; and a negative active material attached to the surface of the substrate; characterized in that the negative active material comprises porous particles, and the porous particles are smaller primary particles and The secondary particles of the metal halide are bonded to the primary particles, and the porous particles have an internal porosity of 10 to 60% by volume and an internal pore having a pore diameter of 1 to 5 nanometers. Preferably, the porous particles have an internal porosity of 30 to 60% by volume and a particle diameter of 0.1 to 100 μm and wherein the metal is selected from one of nickel, iron, copper, cobalt, tungsten, titanium, or a combination thereof. . Preferably, the porous particles are a composite of cerium and nickel pentide. Preferably, the molar ratio of the composite to the metal-lithium compound is 1: 〇.5 to 1:10, more preferably about 1:1 to 1:2. Preferably, the primary particles of the ruthenium and the metal ruthenium constituting the composite have a particle diameter of not more than 5 μm and more preferably not more than 2 μm. Preferably, the composite has an internal porosity of from about 30 to 60% by volume, more preferably from 40 to 50% by volume. Preferably, the porous particles have an inner pore having a pore size of about 2 〇〇 nano 0 8 1332277. Example: High purity elemental powder 矽 (99%, -325 mesh, Aldrich) and nickel (5 μιη) , CERAC) added mechanical alloying to synthesize alloy powder, in which the molar ratio of niobium and nickel is 1:2. Mechanical alloying was carried out using a planetary mill (Fritsch, model Pulverisette P7) and a stainless steel ball mill and ball under an argon (Ar) atmosphere where the ball to powder weight ratio was 14:1 and 〇 .5 weight. /. The stearic acid [CH3(CH2)16COOH] was added as a lubricant. After 16 hours of milling at 400 rpm, an intermediate product containing nickel, ruthenium, and nickel telluride was formed. The product obtained by grinding the powder is placed in 〇.5]y [aqueous solution of nitric acid for 1 hour to invade nickel. The amount of nickel dissolved in the aqueous solution of nitric acid is inductively coupled plasma (ICP) spectroscope (spectroscopy) (Optima, model 3000XL) is added for measurement. Finally, the powder was separated from the aqueous solution of nitric acid, washed with water and 5 Torr in a vacuum oven. The crucible was dried for 6 hours. Thus, a composite secondary particle in which niobium and niobium nickel were bonded was obtained. The negative electrode coating composition is composed of 62% by weight of the above-prepared bismuth and nickel telluride composite particles '30% by weight of a conductive additive and 8% by weight of a binder, wherein the weight percentage is combined Based on the dry weight of the object. The binder is styrene-butadiene rubber (SBR) (Asahi Chemicals, code L1571) and sodium-carboxyl-methylcellulose (SCMC) (DKS International, code WS-C, Collogen) consists of a weight ratio of 1:1. The conductive additive consisted of graphite sheets (graphite 9 1332277 (TIMCAL's code KS6) and nanocarbon black (timcal company code SUPerP, 40 nm) in a weight ratio of 5:1. The negative electrode coating group & The material and deionized water are mixed with χ : i : 2 to obtain a syrup. The polymer is coated on both surfaces of -(4), and the solvent is forged and dried to obtain a total thickness of 64 μm. &, wherein the thickness of the copper foil is 14 microns. The CR2032 button type battery is assembled for electrochemical analysis. The negative electrode is prepared by using the above prepared negative electrode and (4) instead of (4) replacing Shishi and Shixi chemical recording complexes. The positive electrode is lithium drop. The electrolyte is dissolved in ethylene carbonate (ethylene carb〇nate, methyl ethyl carbacetate (MEC) volume ratio J: 2 mixture 1.0 M LiPFy The voltages referred to below are relative to the Li positive electrode unless otherwise specified. The charge/discharge test is performed in a constant current constant voltage (CC-CV) mode between voltage ranges 〇·_ to UVt. The current process uses a constant current of 〇1 mA/mg; The process uses a constant voltage of 〇v and an off current of 〇·03 A/g. The X-ray diffractometer is performed using a Mac-Science/MXp diffractometer and a CuKa light shot. The particle size measurement is performed by light scattering analysis. Porosity and pore size distribution were carried out using a mercury pore size analyzer. The average particle size of the tantalum powder was about 20 μm, and the powder having a particle diameter of 1 to 4 μm was about 77% by volume. After hourly ball milling, the unalloyed nickel is dissolved by dilute nitric acid solution. The purpose of this erosion program is to increase the overall porosity of the powder. Figure 1 shows the X-ray diffraction pattern of the sample before and after the etching process, and the final product is only Residual nickel (Nisi) and Shi Xi. Considering the dissolved amount, the calculated weight ratio of hardening to good is about 2277 is 76/24 (Morbi io/u). After the invasive procedure, the powder The results of the particle size analysis are - a broad particle size distribution, and the powder having a particle size of more than 9% by volume has a particle size of 2 Å). As shown in Fig. 2, scanning electron microscopy and X-ray energy analysis show • Complexes prepared by ball milling and erosion procedures The secondary particles are a porous structure composed of primary particles of less than 2_0 micron and deuterated nickel. Figure 3 shows the analysis results of the pores of the composite particles. The distribution has two peaks, respectively. M and 6 〇〇 Lu is a typical bimodal distribution curve. For a porous material, the peak of S larger hole (600 nm) is mainly attributed to the gap between the particles and the particles. It depends on measuring the tightness of the fashion powder, not the nature of the grain itself. Conversely, the peak of the smaller pore (200 nm) is provided for the pores of the P inside the particle, and the size distribution range is consistent with that observed by the scanning electron microscope. Theoretically, the Gaussian distribution can be used to calculate the total pore volume of the internal pores of the particles separately. The calculation is as follows: 〇 〇 151 cc/go Considering the theoretical density of 矽 and bismuth nickel, the solid of this composite particle # Volume 0.238 cc/g, intraparticle porosity == (particle internal pore volume) / (particle internal pore volume + dry solid volume) The intraparticle porosity can be calculated to be 38 9%. The pure tantalum electrode and the niobium-containing and niobium-doped nickel composite particles of the process of the present invention. The cycle life test capacitance results of the drain electrode are shown in FIG. For the pure Shishi anode material, the flute A ^ β , & first-human charge (lithium migration) capacitance can reach about 33 (9) mAh / g under the condition of current 〇 1A / g, but in the discharge (10) migration process There is an irreversible capacity loss of up to 2/〇, and after only five cycles, the 1332277 charge capacity rapidly decays to about 200 mAh/g; in contrast, the electrode combined by the composite particles exhibits good under the same charge and discharge conditions. The cycle stability 'the first-turn charge capacity is 125G mAh/g, and still retains a capacitance of 540 mAh/g after 5G discharges. The surface structure was observed. Preparation of Samples The analysis of the electrodes after the cycle of the charge/discharge cycle after the analysis was carried out in an argon-filled glove box. It is rinsed and dried in the glove box with diethyl carbonated vinegar ore__, Mc). Observed by the broom microscope, it was found that the thickness of the pure Lixi electrode and the composite particle electrode was 55# Μ micron, and after 10 hours of charging and discharging, the pure Shishi electrode was swallowed to the micron. However, the composite particle electrode only swells (four) 96 micron' to show that the use of composite particles can reduce the volume change of the electrode layer during charge and discharge, and improve the charge and discharge cycle. “ Obviously, the metal that can form the alloy can be selected from the fish, such as nickel, copper, iron, diamond, crane, titanium, etc., the aunts are looking for genus, hunting by the ball milling technology Erosion process
序，均能製借出具有多孔特柯沾说人& I 寻性的複σ物粒子負極材料，以 達到類似的增進充放電循環的— ,,^ 电衣的穩疋性，減少電容量衰減的 效果。 實施例之複合物粒子的理論重量電容量為1298 mAh/g，考慮此複合材料的理論密度為（Μ…^，可計算 出此孔隙度40%的禮人铋姓& & 稷。材枓所提供的理論體積電容量為 3389 mAh/cm3，和現階段齑豐 百权两業化的石墨負極相比較，理論 重量電容量與體積電容量分 里刀別為372 mAh/g和 838 mAh/cm3，此多孔性複合物 物粒子充分地顯現出其優勢。 12 '…厶ΙΊΊ 圖式簡單說明 圖—為本發明實施例中球磨後所得到之複合產物粉體 利用酸液侵蝕處理之前（圖譜（a))與之後（圖譜（15))的χ光 繞射圖譜。 圖二為本發明實施例中由更小的矽一次粒子與矽化錦 一次粒子連結組合而成之本發明多孔複合物二次粒子的掃 晦電子顯微鏡（SEM)照片。 圖二顯示本發明的複合物粒子的孔洞分析結果，其中實 線及數據點為利用水銀孔徑儀測出之孔徑分佈；虛線是利 用尚斯分佈曲線分解出之粒子内（較小孔）與粒子外（較 大孔）孔洞分佈曲線。 圖四為利用純矽粒子及本發明的複合物粒子所製備的 、°的充放電循環測試結果’顯示殘餘電容量與循環次數 的關係。 13In order to reduce the stability of the electro-coating and reduce the capacitance of the composite material, the composite material of the complex σ particles with porous Teko The effect of attenuation. The theoretical weight capacity of the composite particles of the examples is 1298 mAh/g, and considering the theoretical density of the composite material is (Μ...^, the porosity of 40% of the ritual&&& The theoretical volumetric capacity provided by 枓 is 3389 mAh/cm3. Compared with the graphite anodes of the two industries in the current stage, the theoretical weight capacity and volume capacitance are 372 mAh/g and 838 mAh. /cm3, the porous composite particles fully exhibit their advantages. 12 '... 厶ΙΊΊ Illustrated diagram - in the embodiment of the present invention, the composite product powder obtained after ball milling is treated with acid etching ( Graph (a)) and subsequent (Map (15)) calender diffraction pattern. Figure 2 is a porous composite of the present invention in which the smaller primary particles and the primary particles of the bismuth are combined in the embodiment of the present invention. Broom Electron Microscopy (SEM) photograph of secondary particles. Figure 2 shows the results of pore analysis of the composite particles of the present invention, wherein the solid line and the data point are pore size distributions measured by a mercury aperture analyzer; Curve division The distribution curve of the pores (small pores) and the outer pores (large pores) of the particles. Figure 4 shows the results of the charge and discharge cycle test prepared by using pure cerium particles and the composite particles of the present invention. The relationship between capacity and number of cycles. 13