1323522 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種適用於製作電池之正極的材料， 特別是指一種適用於製作二次電池之正極的複合材料及以 其所製得的電池。 【先前技術】 隨著電子產品的多元化發展’使得可攜式能源的需求 與曰俱增，例如消費性電子產品、醫療器材、電動腳踏車 、電動汽車、電動手工具等領域，都需要可攜式電源以作 為其電力來源。目前可攜式能源則以能夠重複使用的二次 電池應用較為廣泛，而在現有二次電池種類中，因鋰離子 二次電池具有高體積比電容、無污染、循環充放特性良好 ’且無記憶效應等優點較具發屐潛力。 又’影響鋰離子二次電池的性能表現之因素，以其用 以製作正極的材料較為關鍵，在已知的用以製作電池之正 極的材料中，因為磷酸鋰鐵化合物或與其相同結構之同性 質化合物，例如LiMP04，Μ為錳（Μη)、鈷（C〇)、鎳（ Ni )等過渡金屬（以下將磷酸鋰鐵化合物及其同性質化合 物一併簡稱為類磷酸鋰鐵化合物），具有良好之電化學特徵 、無環境污染、安全性較佳、原材料來源豐富、比容量高 、循環性能及熱穩定性好且充放電效率高等優點，而被認 為是極具應用潛力的鋰離子電池正極材料之一。 然而，目前已知的類磷酸鋰鐵化合物的電化學性質與 理論值仍有一些差距。以電容量為例，類磷酸鋰鐵化合物 5 1323522 之理論值可達17〇 mAh/g，但是美國專利案us 5，㈣，382所 揭露的一種磷酸鋰鐵化合物之電容量僅約120 mAh/g，遠低 於理娜值。為了改善磷酸鋰鐵化合物的電容量特性，大都 在維持化合物的橄视;s結構或NASI⑽結構下利用其他 元素部分取代或全部取代碟酸鐘鐵化合物中的鐘、鐵或碟 等兀素以增加電容量’纟中又以取代鐵金屬較為常見例 如美國專利案us 6,716,372、us 6,8i5，i22等。由於用以取 代鐵金屬的元素通常較不易取得，使得原料成本較高以 產業應用的成本考量仍受到相當的限制。 此外，美國專利US 6,6；32,566揭露利用提高鱗酸鐘鐵 化合物粉末之比表面積以利於u+於材料中的擴散，藉而可 乂提同％今置。雖然其實施例所記載之電容量可達約 163mAh/g，但其化合物粉末仍然具有粒徑較大且分布不均 勻，故無法在高電流下進行充放電動作的缺點，且從其實 刼例之資料計算，電池的充放電速率約為i/37 c，在實際 應用上仍顯緩慢，還有再改進的空間。 因此，申請人於2005年5月1Q日在中華民國提出申 請之申請案號94115023發明專利案’提供一種製作具有撖 k石結構的UxMyP〇4化合物的方法，步驟是將 離子來源在溶液中混合，再將溶液乾燥得一起始物，將該 起始物在一含有碳微粒的非氧化性氣氛中進行熱處理，而 製得LixMyP〇4化合物。以該方法製得之LixMyPCMt(合物可 具有較小粒徑且分布均勻的粉末。 【發明内容】 6 1323522 本發明即是依據前申請案說明書所揭露之利用含碳微 粒的非氧化性氣氛進扞敎虚 成進灯熱處理，以適$的碳微粒將反應起 始物中的M3+還原成Μ2+ 兹 制 成Μ猎而製仟一具有橄欖石結構的 LWCMt合物的技術内容為基礎進—步研發而完成者。 由於本發明係在含礙微粒的非氧化性氣氛中進行熱處 理，故可利用氣氛中之碳微粒抑制起始物在熱處理過程中 進行晶粒成長，使得所製成之化合物粉末具有奈米級粒徑 的-次粒子（Pd職y particles)’同時，在熱處理過程中會 有少量的碳微粒㈣附著於部分—次粒子的表面並進一 步由該等-次粒子與混掺在該等—次粒子之間的碳形成含 有粒徑可達1微米（μηι)以 — -人粒子（seconda particles)之複合材料粉末。 以該複合材料粉末作為製作二次電池之正極的材料時 ’由於該複合材料中化合物的一次粒子之間混換有碳故 可增加W嵌入及脫嵌過程中的導電性，而且，呈有太 -次粒子與微米級二次粒子的粉末具有較大的比表二、. 故能有效增加電池的電容量。此外，由於該複合材料:末 具有粒徑較大的二次粒子且粒經分布均句，容易與1323522 IX. Description of the Invention: [Technical Field] The present invention relates to a material suitable for producing a positive electrode of a battery, and more particularly to a composite material suitable for the positive electrode of a secondary battery and prepared therefrom battery. [Prior Art] With the diversified development of electronic products, the demand for portable energy sources has increased, such as consumer electronics, medical equipment, electric bicycles, electric vehicles, electric hand tools, etc. Power supply as its power source. At present, portable energy sources are widely used in reusable secondary batteries, and in the existing secondary battery types, lithium ion secondary batteries have high volumetric specific capacitance, no pollution, and good cycle charge and discharge characteristics. The memory effect and other advantages are more promising. Moreover, the factors affecting the performance of the lithium ion secondary battery are critical for the material used to make the positive electrode. Among the known materials for making the positive electrode of the battery, the lithium iron phosphate compound or the same structure is the same. a compound such as LiMP04, a transition metal such as manganese (Μη), cobalt (C〇), or nickel (Ni) (hereinafter, a lithium iron phosphate compound and its isomorphous compound are collectively referred to as a lithium iron phosphate-like compound), Good electrochemical characteristics, no environmental pollution, better safety, rich raw material source, high specific capacity, good cycle performance and thermal stability, high charge and discharge efficiency, etc., and is considered to be a probable lithium ion battery positive electrode. One of the materials. However, there are still some differences between the electrochemical properties of currently known lithium iron phosphate-like compounds and theoretical values. Taking the capacity as an example, the theoretical value of the lithium iron phosphate-like compound 5 1323522 can reach 17 〇 mAh/g, but the capacity of a lithium iron phosphate compound disclosed in U.S. Patent No. 5, (4), 382 is only about 120 mAh/ g, far below the value of Lina. In order to improve the capacity characteristics of lithium iron phosphate compounds, most of them are used to maintain the compound's oligo; s structure or NASI (10) structure to replace or completely replace the halogen, such as a clock, iron or dish, in the acid of the bell acid. It is more common to replace the iron metal in the capacity '纟, for example, US Patent Nos. 6,716,372, us 6, 8i5, i22, and the like. Since the elements used to replace the iron metal are generally less accessible, the cost of the raw materials is still relatively limited in terms of cost considerations for industrial applications. In addition, U.S. Patent No. 6,6,32,566 discloses the use of an increase in the specific surface area of a scaly bell powder compound powder to facilitate the diffusion of u+ into the material, thereby making it possible to provide the same amount. Although the capacitance described in the examples can reach about 163 mAh/g, the compound powder still has a large particle size and uneven distribution, so that it cannot be charged and discharged at a high current, and According to the data calculation, the charge and discharge rate of the battery is about i/37 c, which is still slow in practical application, and there is room for improvement. Therefore, the applicant's application No. 94115023 in the Republic of China on May 1st, 2005, provides a method for preparing a UxMyP〇4 compound having a 撖k stone structure by mixing an ion source in a solution. Then, the solution is dried to obtain a starting material, and the starting material is heat-treated in a non-oxidizing atmosphere containing carbon particles to prepare a LixMyP〇4 compound. The LixMyPCMt obtained by the method can have a powder having a small particle size and a uniform distribution. [Invention] 6 1323522 The present invention is a non-oxidizing atmosphere using carbonaceous particles disclosed in the specification of the prior application. The heat treatment of 捍敎虚成 into the lamp is based on the technical content of the olivine-structured LWCMt compound prepared by reducing the M3+ in the reaction starting material to Μ2+. Since the present invention is subjected to heat treatment in a non-oxidizing atmosphere containing particles, the carbon particles in the atmosphere can be used to suppress the grain growth of the starting material during the heat treatment, so that the prepared compound powder At the same time, there are a small amount of carbon particles (4) attached to the surface of the partial-subparticles during the heat treatment and further by the secondary particles and the blending The carbon formation between the secondary particles includes a composite powder having a particle size of up to 1 micron (μηι) with a second particle. The composite powder is used as a secondary material. When the material of the positive electrode of the pool is used, the conductivity of the W intercalation and deintercalation process is increased due to the carbon exchange between the primary particles of the compound in the composite material, and the presence of the Tai-sub particles and the micro-order secondary particles are also present. The powder has a larger ratio than Table 2. Therefore, the capacitance of the battery can be effectively increased. In addition, since the composite material has secondary particles having a large particle diameter and the particles are uniformly distributed, it is easy to
及溶劑均勻混合，且直接& # & + 。J 土佈方、屯池極板即具有良好的附 者性’並可降低團聚現象，故能增加充放電速率及減少= 充放電現象，也更有利於電池之電極的製作，同時可 電池壽命。 、 因此’本發明之目的即是為提供一種適用於製作二a 電池之正極的複合材料，复伤s执士， 太 其係主粉末狀並具有撖欖石結構 7 或/及鈉石夕康（NASIC0N)結構，且該粉末具有作為基質之 A3xM2y(P〇4)3化合物的奈米級粒徑之—次粒子，及由該等一 次粒子與附著在部分-次粒子表面上之少量的碳所形成之 粒徑大於Ιμχη的二次粒子。其中，一次粒子之粒徑以介於 1〇〜奈米（nm )為宜’而二次粒子之粒徑以介於 ΜΟμ.為佳。再者，該複合材料粉末具有介於5.平方 么尺/克（m/g)的比表面積。 本發明之另一目的是提供一種二次電池，該二次電池 包含一負電極、一電解質及一由一上述複合材料製成之正 電極。 上述A3xM2y(P〇4)3中，八為選自鐘⑴）、納（Na)、鉀 (K)、鍵（Be)、鎮（Mg)、删（B)及紹⑺）令之至少 -者；M S選自銳（Sc)、鈦（Ti)、鈒⑺、鉻（c〇、猛 (Μη)、鐵（Fe)、# (c。）、錄（Ni)' 銅（…、辞 ％ )、釔⑺、鍅（Zr)、鈮（Nb)、|§ (M〇)、鈹（Be)、鎖 (Mg)、好（Ca)、錄（Sr)、蝴（B)、紐（⑷鍺（以） 、錫（Si〇及鎵（Ga)中之至少—者；且〇<山2 , U.6 ’但其組成的元素並不以前述所列元素為限。 該複合材料的製造方法可以前申請案為基礎，依實際 需求選擇可提供組成複合材料之離子來源的材料依適當 比例均勾混合於溶液中’再將該溶液乾燥製得一起始物， 將該起始物置於含碳微㈣非氧化性氣氛中以糊〜刪。c 的溫度’熱處3 6〜48小時’即可製得具有作為基質之 A3xM2y(P〇4)3化合物的奈米級粒徑之—次粒子，及由該等一 次粒子與附著在部分一 粒徑大於〜的-Μ ; 量的碳所形成之 μ的人粒子之複合材料粉末。 更二Γ也’在溶液中混合適量含碳化合物及/或碳粉， /、有抑制晶粒成長的較佳效 ^ ^ X , ^的妷亦可成為該 D '之碳的另—來源。前述含碳化合物可為多質子 有機酸（例如;^ g 0 Λ*. ^ 了檬酸、卓酸、酒石酸、乳酸、對苯二甲酸 、乙二胺四乙酸（ethyIenediaminetetraacetic acid、而A) •、醋酸等）及/或糖類（例如嚴糖、乳糖、葡萄糖、寡糖等） ••可為乙炔杈、奴黑、介穩相球狀碳（仏⑽卩以“ Carbon Micro Beads ’ MCMB)、別啊 p 及/或石墨碳粉。 另外’乾燥方式可為供乾法、超音波喷霧乾燥法、噴 霧乾燥法、燃燒噴霧乾燥法、冷凍乾燥法、真空乾燥法、 過濾乾燥法、噴霧熱裂解法等。 除了前述先形成大粒徑之二次粒子再裂解形成一次粒 子的製造方法之外，亦可先形成一次粒子，再由一次粒子 聚集形成二次粒子。此製法與前述不同處在於將混合溶液 乾燥形成起始物後，將該起始物置於含碳微粒非氧化性氣 氛中以550。(：〜60(TC的溫度煆燒（calcining ) 2〜24小時，接 著將瑕燒後的起始物進行混合造粒製程，再將球磨混合後 的漿料乾燥’之後，將乾燥後的粉末置於含碳微粒的非氧 化性氣氛中，以400〜900eC的溫度，燒結6~48小時，亦可 衣付具有作為基質之A3xM2y(P〇4)3化合物的奈米級粒徑之 一次粒子，及由該等一次粒子與附著在部分一次粒子表面 上之少量的碳所形成之粒徑大於1 μπη的二次粒子之複合树 料粉末。 該複合材料粉末具有奈米級的一次粒子及由該等一 次粒子所形成之微米級且粒徑分布―致的二次粒子，可與 多種的黏結劑及溶劑m合’尤其可❹水溶性黏結劑 並以去離子水為溶劑，而不像現有之材料僅能使用聚偏二 乱乙細（PolyVinyliDene Fluoride，PVDF)及 N 甲基四石比 錢酮.(N-methyI_pyrr()lidc)ne，NMp)為點結劑及溶土劑而 且將該複合材料與黏結劑混合後直接塗佈於電池極板即具 有良好的附著|生，因此’以該複合材料製作二次電池的正 電極’可以簡化製程步驟及降録結劑與溶劑的材料成本 ’有助於商業化的量產製造。 電解質等組 項技術領域 電解質，在 以該複合材料製得的正電極再與負電極和 ^即可製得二次電池。電池的製作為熟習該 者所熟知’可依實際需求搭配適當的負電極與 此不再詳細描述。 【實施方式】 掃描式電子顯微鏡（SEM) : Hitachi m〇dei s_35()()v 2·粒徑分析儀：H〇RIBA，LA-910。 3. 充放電機：Maccor 4000 〇 4. 比表面積測試：ASAP 2010。 以下將藉實施例更詳細地說明本發明之内容。And the solvent is evenly mixed, and directly &#& + . J Tubufang and Dianchi plate have good attachment characteristics and can reduce the phenomenon of agglomeration, so it can increase the charge and discharge rate and reduce = charge and discharge phenomenon, and is more conducive to the production of battery electrodes, and battery life. . Therefore, the object of the present invention is to provide a composite material suitable for the production of a positive electrode of a two-a battery, which is a general-purpose powder and has a sapphire structure 7 or/and a sodium stone. (NASIC0N) structure, and the powder has a nano-particle size-sub-particle of the A3xM2y(P〇4)3 compound as a matrix, and a small amount of carbon attached to the surface of the partial-subparticle by the primary particles The formed secondary particles have a particle size larger than Ιμχη. Among them, the primary particles have a particle diameter of from 1 〇 to nanometer (nm), and the secondary particles have a particle diameter of preferably ΜΟμ. Further, the composite powder has a specific surface area of 5. square feet per gram (m/g). Another object of the present invention is to provide a secondary battery comprising a negative electrode, an electrolyte, and a positive electrode made of the above composite material. In the above A3xM2y(P〇4)3, eight are selected from the group consisting of clock (1), nano (Na), potassium (K), bond (Be), town (Mg), delete (B), and Shao (7). MS is selected from the group consisting of sharp (Sc), titanium (Ti), niobium (7), chromium (c〇, Μ ()η), iron (Fe), # (c.), recorded (Ni)' copper (..., the word % ), 钇 (7), 鍅 (Zr), 铌 (Nb), |§ (M〇), 铍 (Be), lock (Mg), good (Ca), recorded (Sr), butterfly (B), New ((4)锗 (to), tin (Si〇 and gallium (Ga) at least one of; and 〇 <Mountain 2, U.6 ' but the elements of its composition are not limited to the elements listed above. The manufacturing method can be based on the previous application, and the material which can provide the ion source constituting the composite material is selected according to the actual demand, and is mixed in the solution according to an appropriate ratio. Then the solution is dried to obtain a starting material, and the starting material is placed. In the carbon-containing micro (tetra) non-oxidizing atmosphere, the temperature of the paste ~ deleting C is 'heated for 3 6 to 48 hours' to obtain the nanometer particle size of the A3xM2y(P〇4)3 compound as a matrix. Secondary particles, and by the primary particles and attached to the portion of a particle size greater than ~ - Μ ; The amount of carbon formed by the composite particles of human particles of μ. The second is also 'mixed with the appropriate amount of carbon-containing compounds and / or carbon powder in the solution, /, has the best effect of inhibiting grain growth ^ ^ The enthalpy of X, ^ may also be another source of the carbon of the D'. The aforementioned carbon-containing compound may be a polyprotic organic acid (for example; ^ g 0 Λ*. ^ citric acid, acid, tartaric acid, lactic acid, Ethylene phthalate, ethylenediaminetetraacetic acid (A), acetic acid, etc. and/or sugars (eg, sugar, lactose, glucose, oligosaccharides, etc.) •• can be acetylene oxime, slave black, metastable Phase spheroidal carbon (仏 (10) “ with "Carbon Micro Beads ' MCMB), other p and / or graphite carbon powder. In addition 'drying method can be dry, ultrasonic spray drying, spray drying, combustion spray Drying method, freeze drying method, vacuum drying method, filtration drying method, spray pyrolysis method, etc. In addition to the above-mentioned method of first forming a large particle size secondary particle to be re-cracked to form primary particles, a primary particle may be formed first. Secondary particle formation to form secondary particles The difference from the above method is that after the mixed solution is dried to form a starting material, the starting material is placed in a carbon-containing fine particle non-oxidizing atmosphere at 550. (: ~60 (TC temperature calcining 2~) After 24 hours, the raw material after the simmering is subjected to a mixing granulation process, and then the slurry after the ball milling is dried, and then the dried powder is placed in a non-oxidizing atmosphere containing carbon particles to 400~ The temperature of 900eC, sintered for 6 to 48 hours, can also be used to coat the primary particles of the nano-sized particle size of the A3xM2y(P〇4)3 compound as a matrix, and the primary particles are attached to the surface of the partial primary particles. The composite tree powder of the secondary particles having a particle diameter larger than 1 μπη formed by a small amount of carbon. The composite powder has nanometer primary particles and micron-sized particle size distribution secondary particles formed by the primary particles, and can be combined with various binders and solvents, especially water-soluble bonding. And use deionized water as solvent, instead of the existing materials, only PolyVinyliDene Fluoride (PVDF) and N-methyI_pyrr()lidc)ne can be used. NMp) is a knotting agent and a lytic agent, and the composite material is directly coated on the battery plate after being mixed with the binder, which has a good adhesion, so that the positive electrode of the secondary battery can be made of the composite material. Simplifying the process steps and reducing the material cost of the binder and solvent 'helps commercial mass production. Electrolyte and other technical fields Electrolyte, a secondary battery can be obtained by using a positive electrode made of the composite material and a negative electrode. The fabrication of the battery is well known to those skilled in the art. The appropriate negative electrode can be used as needed and will not be described in detail. [Embodiment] Scanning electron microscope (SEM): Hitachi m〇dei s_35 () () v 2 · Particle size analyzer: H〇RIBA, LA-910. 3. Charge and discharge machine: Maccor 4000 〇 4. Specific surface area test: ASAP 2010. The contents of the present invention will be described in more detail below by way of examples.
SjkM. 10 1323522 <實施例A > 將0.2莫耳硝酸鐵加至200ml去離子水中溶解，待完全 溶解後加入0.2莫耳的麟酸，再將預先配好的含有ο.〕莫耳 的氫氧化經水溶液l〇0ml加入混合’使溶液中鋰離子：鐵 離子：磷酸根離子依LiFeP〇4的計量比例（ι:1:1)混合， 待完全混合反應後形成一含有pe金屬離子、u+及（p〇4)3-的 溶液，並於溶液中再加入含有草酸〇.252g的1〇〇mi水溶液SjkM. 10 1323522 <Example A > 0.2 mol of ferric nitrate was added to 200 ml of deionized water to dissolve, and after complete dissolution, 0.2 mol of linalic acid was added, and then pre-formed containing ο. Hydrogen peroxide is added to the mixture by adding 〇0ml of the aqueous solution to make the lithium ion in the solution: the iron ion: the phosphate ion is mixed according to the ratio of LiFeP〇4 (1:1), and after the reaction is completely mixed, a pe-containing metal ion is formed. a solution of u+ and (p〇4)3-, and further adding a solution of 2522.5 g of 1〇〇mi aqueous solution to the solution.
’充分攪拌後，再將該溶液乾燥，乾燥後即得一粉末狀的 起始物。 將該起始物置於氧化鋁坩鍋中，再將此坩鍋置於放有 木炭之管狀爐内，使其在通氮氣氛下以7〇(rc熱處理小 時，熱處理過程中木炭在高溫下產生的❹子懸浮物藉由 流動的氮氣載送，使碳微粒摻雜入該起始物的粉末中，而 製得一以磷酸鋰鐵為基質並混摻有碳的複合材料粉末。 <實施例B >After sufficient agitation, the solution was dried and dried to give a powdery starting material. The starting material is placed in an alumina crucible, and the crucible is placed in a tubular furnace in which charcoal is placed, and is subjected to a nitrogen gas atmosphere at 7 Torr (rc heat treatment is small, and charcoal is produced at a high temperature during heat treatment). The hazelnut suspension is carried by flowing nitrogen gas, and carbon particles are doped into the powder of the starting material to obtain a composite powder based on lithium iron phosphate and mixed with carbon. Example B >
實施例B與該實施例A的製法大致相同苴差異之處 在於將賴鐵置換成〇.2莫耳氣化鐵溶於去科〇 ’，、其餘 步驟與έ玄貫施例A相同，制彡圼 IV r# An IJ衣付一以磷酸鋰鐵為基質並混摻 有碳的複合材料粉末β <實施例C > 實施例c與該實施例Α的製法大致相同，盆差里之〆 在於將硝酸鐵置換成〇.2莫耳鐵粉溶於去離子水中4餘: 驟與該實施例Α相同1得-叫⑽鐵為基質並混摻ί 碳的複合材料粉末。 ' 11 <貫施例D > 實施例D與該實施例C的製法大致相同，其差異之處 在於將100 ml草酸水溶液置換成含〇.42g檸檬酸之1〇〇 ml 水溶液’其餘步驟與該實施例C相同，製得一以磷酸鋰鐵 為基質並混推有碳的複合材料粉末。 <實施例E >The method of Example B is substantially the same as that of the embodiment A. The difference is that the iron is replaced by 〇. 2 mole gas is dissolved in the 〇 〇, and the remaining steps are the same as the 施 贯 施 施 ,彡圼IV r# An IJ 付付 A composite material powder based on lithium iron phosphate and mixed with carbon β <Example C > Example c is substantially the same as the preparation method of this example, The trick is to replace the ferric nitrate with 〇. 2 molar iron powder dissolved in deionized water for more than 4: The same as in this example 1 1 - called (10) iron as a matrix and mixed with carbon composite powder. '11 <Example D> Example D is substantially the same as the method of Example C except that 100 ml of an aqueous oxalic acid solution is replaced with a 1 ml aqueous solution containing 〇.42 g of citric acid. In the same manner as in Example C, a composite powder in which lithium iron phosphate was used as a matrix and carbon was mixed was prepared. <Example E >
實施例E與該實施例D的製法大致相同，其差異之處 在於〉谷液中更加入0.1 g之葡萄糖，其餘步驟與該實施例D 相同，製得一以磷酸鋰鐵為基質並混摻有碳的複合材料粉 末。 <實施例F > 實施例F與該實施例D的製法大致相同，其差異之處 在於溶液中更加入lg之蔗糖，其餘步驟與該實施例D相同 ’製得一以磷酸鋰鐵為基質並混摻有碳的複合材料粉末。 〈實施例G > 實施例G與該實施例D的製法大致相同，其差異之處 在於將實施例D中0.2莫耳鐵粉以0.196莫耳鐵粉、0.002 莫耳MgCh、0.002莫耳AICI3取代，其餘步驟與該實施例 D相同’製得一以LiFe0.98Mg0.0]Al0.01p〇4為基質並混 摻有碳的複合材料粉末。 <實施例Η > 貫施例Η與該實施例D製備起始物的步驟相同，實施 例Η與實施例D不同之處在於其後之熱處理步驟。 實施例Η是將乾燥後的起始物置於氧化鋁坩鍋中，再 12 1323522 將此㈣置人管狀爐中並於氮氣氣氛下以5t/min之升溫速The preparation method of Example E is substantially the same as that of the embodiment D, and the difference is that more than 0.1 g of glucose is added to the solution, and the rest of the steps are the same as that of the example D, and a lithium iron phosphate matrix is prepared and mixed. Carbon composite powder. <Example F > Example F is substantially the same as the method of Example D, except that lg of sucrose is added to the solution, and the remaining steps are the same as in the example D. The matrix is mixed with a carbon composite powder. <Example G > Example G was substantially the same as the method of Example D, except that 0.2 mol of iron powder in Example D was 0.196 mol iron powder, 0.002 mol MgCh, 0.002 mol AICI3. Instead of the same procedure as in the example D, a composite powder in which LiFe0.98Mg0.0]Al0.01p〇4 was used as a matrix and mixed with carbon was prepared. <Examples> Example 贯 The procedure for preparing a starting material in this Example D was the same, and Example Η was different from Example D in the subsequent heat treatment step. In the embodiment, the dried starting material is placed in an alumina crucible, and then 12 1323522 is placed in a tubular furnace and heated at a rate of 5 t/min under a nitrogen atmosphere.
度升溫至_m 4小時後’再以爐冷方式降至室溫， 完成假燒。將坂燒後所得的粉末與2 wt%的聚乙稀醇（pvA )水溶液以固液比4〇:60於球磨機中進行混合分散三小時的 造粒製孝呈’將戶斤形成的漿狀溶液以噴霧乾燥法乾燥並將 乾燥後的粉末置於氧化紹掛鋼中，再將此掛銷置於放有木 炭之管狀爐内，木炭在高溫下產生的碳粒子懸浮物藉由流 動的氮氣载送，使經過煆燒的起始物粉末在含碳微粒的通 氮氣氛下以80CTC熱處理8小時進行燒結，再以爐冷方式降 至室溫’製得一以鱗酸經鐵為|質並混推有碳的複合材料 粉末。 發明效果 粒徑分析 參閱圖1與圖2，將實施例D所製得之複合材料粉末以 掃描式電子顯微鏡觀察’由5000倍（圖υ及1〇〇〇〇倍（ 圖2)之放大影像顯示，實施例D之複合材料粉末是由均勻 的50〜10〇nm左右的一次粒子團聚，而形成大於i〇(jm以上 之二次粒子。 另取實施例D之複合材料粉末10克，以粒徑分析儀分 析其粒徑分佈。如圖3所示，粒子分佈範圍（⑴⑽以以〇η % ):D10 約為 33.7μηι，D20 約為 27.6μηι，D30 約為 23 8μηι ，D50 約為 18.3μηι，D80 約為 1ΐμπι，D90 約為 7 〇Jim ,由 D50之值可推知實施例D之複合材料粉末的二次粒子為 級尺寸’且為單一峰值’顯示其粒徑分佈相當一致。 13 1323522 圖4為實施例Η所製得的複合材料粉末以掃描式電子 顯微鏡觀察之放大5000倍影像，其影像與圖1相似，可看 出實施例Η所製得的複合材料粉末也是由均勻的50〜100nm 左右的一次粒子團聚，而形成大於10 μηι以上之二次粒子。 比表面積分析 將實施例Ε製得之複合材料粉末，利用氮氣等溫吸附/ 脫附曲線原理計算其樣品於77Κ溫度下之BET (Brunauer-Emmett-Teller )比表面積。由測試結果可知，其比表面積可 達38.42 m2/g。此外，將實施例Η製得之複合材料粉末，以 同樣方法測其比表面積可達39 m2/g。與美國專利案US 6,632,566之實施例相較，該案於700°C熱處理後所得的比 表面積僅約2.5 m2/g，本發明之複合材料粉末的比表面積有 顯著的提昇。 充放電循壤測試 分別將實施例F、G、Η製得之複合材料粉末與乙块碳 黑和聚偏二氟乙烯（PVDF)依重量比83 : 10 : 7之比例混合 成漿料，再均勻塗佈於鋁箔上。經烘乾後，製成適當之正 極試片，並與鋰金屬組成2032鈕型扣電池，以0.2C之充放 電速率於2.8V〜4.0V之間，利用充放電機進行充放電循環 測試。測試結果分別示於圖5、圖6、圖7。 如圖5所示，實施例F製得之複合材料粉末製成正極 片後，其初始電容量可達152mAh/g，且於10次循環後， 其電容量仍可維持100%以上。圖6顯示，實施例G製得之 複合材料粉末製成正極片後，其電容量高達167mAh/g 14 1323522 ，接近此材料之理論電容量170mAh/g。而圖7所示，實施 例Η製得之複合材料粉末製成之正極片經10次充放電後， 其電容量可達162mAh/g。由此可知，本發明由小粒徑之一 次粒子組成大粒徑之二次粒子的粉末型態，具有高比表面 積而有助於提升電容量，並於製作電極時，有利於漿料之 分散與塗佈。 全電池測試 將實施例F所製得之複合材料粉末分別以不同的溶劑 及黏結劑混合塗佈於極板上，再製成全電池，並以不同的 充放電速率測試其電性。 電池1 將該複合材料粉末與聚偏二氟乙烯（PVDF )、碳粉依 85:12:3比例充分混合於NMP溶劑，其黏度為4000mPa.s， 再塗佈於鋁箔極板並經100°C烘乾後，其厚度為132um，且 完全無掉粉現象，將此極板裁切以組成方形電池。該電池 所用負極材料為碳材，而電解液為含有LiPF6 lmol/L的碳 酸乙烯醋/碳酸二乙自旨（ethylene carbonate/diethyl carbonate ，EC/DEC)溶液。再分別以 0.2C、0.5C、1C、2C、3C 及 5C等不同的充放電速率測試。如圖8所示（圖中曲線以橫 向段視之，由上至下分別為0.2C、0.5C、1C、2C、3C及 5C之放電速率的曲線），該電池在不同充放電速率，都能夠 有效充放電，而且於5C放電時的電容量仍有0.2C放電電 容量的87%，可知本發明由小粒徑之一次粒子組成大粒徑 之二次粒子的粉末型態，具有易於塗佈於極板上之優點， 15 1323522 才能達到如此高充放電速率。 電池2 將該複合材料粉末與苯乙烯-丁二烯橡膠（styrene-butadiene rubber ’ SBR )、 碳 酸甲基 纖維素 （Carboxy methyl cellul〇se，CMC)及碳粉依 95..1.5:0.5:3 比例充 分混合於去離子水中，其黏度為4000mPa.s，再塗佈於鋁羯 極板並經80°C烘乾後，其厚度為200 um，且完全無掉粉現 象’將此極板裁切以組成1865〇電池。該電池所用負極材 料為碳材，而電解液為含有LiPF6 lmol/L的EC/DEC溶液 。再分別以0.5C、1C、2C、5C及8C等不同的充放電速率 測試。如圖9所示（圖中曲線以橫向段視之，由上至下分 別為0.5C、1C、2C、5C及8C之放電速率的曲線），該電 池在不同充放電速率，都能夠有效充放電，而且於8c放電 時的電容量仍有0.5C放電電容量的9〇%。 由电池1、2可知，本發明由小粒徑之一次粒子組成大 粒徑之二次粒子的粉末型態具有易於塗佈於極板上之優點 ，並且以不同的溶劑和黏結劑，都能有效將本發明之複合 材料粉末塗佈於極板上，尤其能混合於去離子水中，為現 有技術無法達成，故具有極佳的產業利用性。 而且 歸納上述，本發明適用於製作二次電池之正極的複入 材料，其粉末具有奈米級的一次粒子，並以該等一次粒= 組成微米級且粒徑分布一致的二次粒子’可以大幅提昇材 料之比表面積，進而具有增加電容量的效果，同時能夠以 不同的溶劑與點結劑塗佈於極板上，不僅方便製作， 16 1323522 所形成的電池可具有高充放電速率、高電容量，且能減少 過充電或過放電的情況而增加電池壽命，確實能達成本發 明之目的。 惟以上所述者，僅為本發明之較佳實施例而已，本不 能以此限定本發明實施之範圍，即大凡依本發明申請^利 範圍及發明說明内容所作之簡單的等效變化與修飾 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1是一 SEM影像，說明本發明適用於製作二次電也 之正極的複合材料之實施例D所製得的粉末之二次粒子. 料粉影像，說明該實施例^製得的複合材 圖3是一粒徑分析圖’說明 材料粉末之粒徑分布； 尸斤衣付的硬合 圓4是一 SEM影像，說 複合材料粉末之二次粒子； 月之只^所製得的 發明2是—充放電循環次數與電容量之關_，說明本 放電:=所製得的複合材料Μ — 試 圖6是一電容量與電麈之關係圖，說明 G所製得的複合材料粉末製成正極片後的充放電循= 施例圖Η 7疋另一 4量與電壓之關係圖，說明本發明之實 所製得的複合材料粉末製成正極片後的充放電測試 17 1323522 圖8是另一電容量與電壓之關係圖，說明本發明之實 施例F所製得的粉末製成全電池後的充放電循環測試；及 圖9是另一電容量與電壓之關係圖，說明本發明之實 施例F所製得的粉末與不同黏結劑混合製成全電池後的充 - 放電測試。 _* 【主要元件符號說明】 無 18After heating to _m for 4 hours, the furnace was cooled down to room temperature to complete the sinter. The powder obtained after calcination and the 2 wt% aqueous solution of polyvinyl alcohol (pvA) are mixed and dispersed in a ball mill at a solid-liquid ratio of 4 〇:60 for three hours to form a granule. The solution is dried by spray drying and the dried powder is placed in a oxidized steel, and the pin is placed in a tubular furnace in which charcoal is placed, and the carbon particle suspension generated by the charcoal at a high temperature is passed through a flowing nitrogen gas. Carrying, the calcined starting material powder is sintered by heat treatment at 80 CTC for 8 hours under a nitrogen-containing atmosphere containing carbon particles, and then cooled to room temperature by furnace cooling to obtain a scalar acid by iron. And mix the carbon composite powder. EFFECTS OF THE INVENTION Particle size analysis Referring to FIG. 1 and FIG. 2, the composite material powder obtained in Example D was observed by a scanning electron microscope 'magnified by 5000 times (magnified by 1 〇〇〇〇 and 1 ( (Fig. 2)) It is shown that the composite powder of Example D is agglomerated by a uniform primary particle of about 50 to 10 〇 nm to form a secondary particle larger than i 〇 (jm or more. Further, 10 g of the composite powder of Example D is used. The particle size analyzer analyzes the particle size distribution. As shown in Fig. 3, the particle distribution range ((1)(10) to 〇η%): D10 is about 33.7μηι, D20 is about 27.6μηι, D30 is about 23 8μηι, and D50 is about 18.3. Ηηι, D80 is about 1 ΐμπι, D90 is about 7 〇Jim, and it can be inferred from the value of D50 that the secondary particles of the composite powder of Example D are of the grade size 'and the single peak' shows that the particle size distribution is quite uniform. 13 1323522 4 is a magnified 5000-fold image of the composite powder prepared in Example 以 by a scanning electron microscope, and the image thereof is similar to that of FIG. 1, and it can be seen that the composite powder obtained in the example 也是 is also uniform 50. ~100nm or so The particles agglomerated to form secondary particles larger than 10 μηι. Specific surface area analysis The composite powder prepared in Example , was subjected to the BET (Brunauer- at 77 °C) using a nitrogen isotherm adsorption/desorption curve principle. Emmett-Teller) specific surface area. From the test results, the specific surface area can reach 38.42 m2 / g. In addition, the composite powder prepared in the example 测 can be measured to have a specific surface area of 39 m 2 /g. In comparison with the examples of U.S. Patent No. 6,632,566, the specific surface area obtained by heat treatment at 700 ° C is only about 2.5 m 2 /g, and the specific surface area of the composite powder of the present invention is remarkably improved. The composite powders prepared in Examples F, G, and Η were mixed with a block of carbon black and polyvinylidene fluoride (PVDF) in a ratio of 83:10:7 to a slurry, and then uniformly coated on an aluminum foil. After drying, a suitable positive electrode test piece is prepared, and a 2032 button type buckle battery is formed with lithium metal, and the charge and discharge cycle is tested by a charge and discharge machine at a charge and discharge rate of 0.2 C between 2.8 V and 4.0 V. .Test Results 5, Fig. 6, and Fig. 7. As shown in Fig. 5, after the composite material powder obtained in Example F is made into a positive electrode sheet, the initial electric capacity can reach 152 mAh/g, and after 10 cycles, The capacitance can still be maintained above 100%. Figure 6 shows that after the composite powder prepared in Example G is made into a positive electrode sheet, its capacitance is as high as 167 mAh/g 14 1323522, which is close to the theoretical capacity of the material of 170 mAh/g. As shown in FIG. 7, the positive electrode sheet made of the composite material powder obtained in the example Η has a capacity of 162 mAh/g after 10 times of charge and discharge. It can be seen that the present invention consists of a small particle size primary particle composed of a large particle size secondary particle powder type, which has a high specific surface area and contributes to an increase in capacitance, and facilitates dispersion of the slurry when the electrode is fabricated. With coating. Full Battery Test The composite powders prepared in Example F were mixed and applied to the plates with different solvents and binders, and then made into full cells, and their electrical properties were tested at different charge and discharge rates. Battery 1 The composite powder was thoroughly mixed with polyvinylidene fluoride (PVDF) and carbon powder in a ratio of 85:12:3 to NMP solvent with a viscosity of 4000 mPa·s, and then coated on an aluminum foil plate and passed through 100°. After drying C, the thickness was 132 um, and there was no powder drop at all, and the plate was cut to form a prismatic battery. The negative electrode material used in the battery was a carbon material, and the electrolyte was a solution containing 1 mol/L of LiPF6/ethylene carbonate/diethyl carbonate (EC/DEC). Then, they were tested at different charge and discharge rates of 0.2C, 0.5C, 1C, 2C, 3C and 5C. As shown in Figure 8 (the curve in the figure is viewed in the transverse direction, the curve of the discharge rate of 0.2C, 0.5C, 1C, 2C, 3C and 5C from top to bottom respectively), the battery is at different charge and discharge rates, It can effectively charge and discharge, and the capacitance at the time of 5C discharge still has 87% of the 0.2C discharge capacity. It is understood that the present invention consists of a small particle size primary particle composed of a large particle size secondary particle powder type, which is easy to apply. The advantage of cloth on the plate, 15 1323522 can achieve such a high charge and discharge rate. Battery 2 The composite powder with styrene-butadiene rubber 'SBR, methyl cellulose (Carboxy methyl cellul〇se, CMC) and carbon powder 95..1.5:0.5:3 The ratio is fully mixed in deionized water, the viscosity is 4000mPa.s, and then coated on the aluminum crucible plate and dried at 80 ° C, the thickness is 200 um, and there is no powder drop phenomenon. Cut to form a 1865 〇 battery. The negative electrode material used for the battery was a carbon material, and the electrolyte was an EC/DEC solution containing LiPF6 lmol/L. Then, they were tested at different charge and discharge rates of 0.5C, 1C, 2C, 5C and 8C. As shown in Figure 9 (the curve in the figure is viewed in the transverse direction, the curve of the discharge rate of 0.5C, 1C, 2C, 5C and 8C from top to bottom respectively), the battery can be effectively charged at different charge and discharge rates. The discharge was discharged, and the capacitance at the time of discharge at 8c was still 9% of the 0.5 C discharge capacity. It can be seen from the batteries 1 and 2 that the powder form of the secondary particles of large particle size composed of primary particles having a small particle size has the advantage of being easily applied to the electrode plate, and can be coated with different solvents and binders. The composite material powder of the present invention can be effectively applied to an electrode plate, and can be mixed especially in deionized water, which is not possible in the prior art, and thus has excellent industrial applicability. Further, in summary, the present invention is applicable to a reconstituted material for producing a positive electrode of a secondary battery, the powder of which has nano-sized primary particles, and the primary particles having the same size as the micro-particles and having the same particle size distribution can be The material surface area of the material is greatly increased, and the effect of increasing the capacitance is further enhanced. At the same time, the solvent and the spotting agent can be applied to the electrode plate, which is not only convenient for fabrication, but the battery formed by 16 1323522 can have a high charge and discharge rate and a high height. The capacity of the battery can be reduced by overcharging or overdischarging to increase the battery life, and the object of the present invention can be achieved. However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the present invention in accordance with the scope of the invention and the description of the invention. It is within the scope of the patent of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an SEM image illustrating a secondary particle of a powder prepared in Example D of a composite material for producing a secondary electrode of a secondary electricity. Figure 3 is a particle size analysis diagram to illustrate the particle size distribution of the material powder; the hard-combined circle 4 of the corpse is an SEM image, said the secondary particles of the composite powder; The invention 2 obtained is - the number of charge and discharge cycles and the capacitance _, indicating that the discharge: = the composite material produced Μ - attempt 6 is a relationship between capacitance and power, indicating that G is produced The charging and discharging cycle of the composite material powder after forming the positive electrode sheet is as follows: Fig. 7 is a diagram showing the relationship between the other four amounts and the voltage, illustrating the charging and discharging of the composite material powder prepared by the invention after the positive electrode sheet is prepared. Test 17 1323522 Figure 8 is a diagram showing the relationship between another capacitance and voltage, illustrating the charge and discharge cycle test after the powder obtained in Example F of the present invention is made into a full battery; and Figure 9 is another capacitance and voltage. Diagram showing the powder obtained in Example F of the present invention After filling with a different binder prepared by mixing whole cell - discharge test. _* [Main component symbol description] None 18