201221469 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種鋰離子二次電池正極材料之製造方 法，特別係關於一種磷酸鋰鐵（LiFePO4)材料之製造方法 以及由該方法製得之磷酸鋰鐵粉末。 【先前技術】 鋰離子二次電池由於具有電壓高、能量密度高、放電 電壓平穩、循環壽命長、無記憶效應和工作溫度範圍寬等 諸多優點，目前已被廣泛應用於各類可攜式裝置中。此外， 在需要高容量、高功率的電動工具、電動自行車及電動汽 車等應用領域中，鐘離子二次電池的發展前景也相當被看 好。 於現有的各類鋰離子二次電池正極材料中，具有橄欖 石晶格結構的磷酸鋰鐵（或稱磷酸鐵鋰）由於有高重量能 量密度、高充放電壽命、高充放電能力、無毒性及低成本 等優點，故已成為最有發展潛力的鋰離子二次電池正極材 料。 目前磷酸鋰鐵之製造方法大致可分成固態法、熱碳還 原法、共沉法及水熱法等。 固態法主要是選取碳酸鋰（Li2C03 )、草酸亞鐵 (FeC204 · 2H20)及磷酸二氫銨（（NH4)H2p〇4；) 一起在溶 劑存在下混合、烘乾，然後再緞燒。因為粉末採固態方式 混合’所以固態法之原料均勻度相對較差。 201221469 熱碳還原法主要是使用含有三價鐵的三氧化二鐵 (Fe2〇3)作為鐵源。在此類製程中，由於鐘、鐵、碟等原 料是以固態的方式混合’所以熱碳還原法會有和固態法一 樣的缺點，即原料混合均勻度較差。 共沉法主要是使用硫酸亞鐵（FeS〇4 )、氫氧化鐘 (LiOH)及磷酸（H3P〇4)作為原料，以氨水調控溶液之 pH值’而使Li、Fe、P等元素產生沉殿。雖然此種製程解 決了混合均勻度不佳的問題，但由於需經多道清洗步驟才 可製成而品質之產品’且存在有廢水處理的問題，故其製 程非常複雜。 ^ 水熱合成法主要是利用在高壓、中溫之條件下材料具 有高溶解度及反應度之特性來製作磷酸鋰鐵，但因為反^ 溫度較低，僅約1〇〇〜200。(：，所以產品之高溫特性相對^ 差。此外，水熱合成法之設備也相對昂貴。 乂 為了針對傳統方法之缺點進行改善，先前技術中曾有 人提出各種不同的固液結合之磷酸鋰鐵製備方法。 舉例而S，中國專利申請案公開第CN101152961號揭 露一種製備磷酸_之方法，其主㈣猶水溶性的三氧 化一鐵纟命性的磷酸二氣鐘、推雜金屬元素的氧化物或 碳韻、在水溶液巾先進行球磨，之後喷霧乾燥得到 類球型粉末，再於_型粉料中二:欠加人碳源，並依序進 仃，磨、第-次锻燒、球磨、過_、第二次锻燒、粉碎、 過篩等步驟。 儘&其說明書中指出該方法可得到高密度、優良黏結 4 201221469 性的填酸鐘鐵材料，但由於碳源需分兩次加人，程序上較 為麻煩，且該方法是先將聚料喷霧造粒製成粉末後，再二 =加t碳源，之後又進行球磨、第—次锻燒、球磨、過韩、 第二二人锻燒、粉碎、過筛等步驟，不僅程序繁瑣’且噴霧 =後：類球型顆粒會因球磨步驟而破碎，造成粉體的顆 :;法控制（由其圖1中可觀察到形狀不規則之顆 粒），故此種方法製成的產品，在後續電池製程的過程 中，並不易控制漿料的黏調度及電極材料的塗佈厚产。 中國專财請案公開第CN1G1355156號揭露；固液 結合製備磷酸鐘鐵的方法，其先將鐘源化合物、鐵源化人 物、鱗酸、璘源化合物及少量碳的有機物前躺體混合，: 後在80至120 γ下烘乾後進行球磨以得到前軀體粉末， 再將前躯體粉末在惰性氣氛或還原氣氛下吹掃，之後加熱 到400至800 〇C，並於恒溫維持3至8小時後冷田， 最後再進行破碎。 乂由於前述製程是以原料混合、烘乾、再球磨的方式製 作前軀體粉末，所以產製出來的磷酸鋰鐵粉末顆粒相冬 小，而會有後續電池製程不易調漿的困擾。此外，由於前 述製程僅添加碳源來增加導電度，而並未加入其他換雜元 素，故最終產品的特性相對較差。 中國專利申請案公開第C N101714 65 8號揭露之製程係 將裡鹽、金屬氧化物和碳源加入磷酸水溶液中，經過反應 得到LiHjO4混合溶液，然後加入奈米級鐵化合物，在球 磨機中球磨，並經過喷霧乾燥，再於惰性氣體保護下在 201221469 _〜卿。c的燒結爐中燒結，最後以水清洗碟酸鐘鐵粉 末，然後在100〜200。(：乾燥。由於前述製程之鐵源指定使 用奈米級鐵化合物，且因煅燒使用推板窯會產生塊狀鬆散 之磷酸鋰鐵，故需以表面處理器將其打碎成顆粒狀物^。 據此，此篇文獻内容除了限制使用的鐵源材料粒度過小 外，還會因後續處理工藝問題使緞燒粉體的粒徑不易控制。 於廣州化工2011年39卷第1〇期之論文「固液結"合一 碳熱還原法製備LiFePOVC材料的研究」中，其同樣在製 程中採用了烘乾再球磨的作法，因此產出的魏鐘鐵粉末 顆粒也偏小而不利調漿，同時因為未添加摻雜元素來提升 導電度，故產品的特性也相對較差。 有鑑於現有技術中已知的各種磷酸鋰鐵製備方法仍有 令人不甚滿意之處，有必要提出一種製程簡單、製造成本 便宜且可工業化量產之方法，以利製造出具有高克容量、 高倍率放電性能及循環壽命長的產品。 【發明内容】 本發明之主要目的之一，在於提出一種碟酸鐘鐵材料 之製造方法，相較於現有技術中的其他方法，其具有製程 簡單、製造成本便宜且可工業化量產之優點。 本發明之另一主要目的’在於利用半化學法來改良熱 碳還原法以製備磷酸鋰鐵，並達成整個製程與固態法製程 一樣簡單真實施成本便宜之優點。 本發明之方法主要包括以下步驟：（A)依下列規則選 201221469 擇微米等級之碟源 原料：若該鐵源為、鐘源及含有三價鐵化合物之鐵源作為 為非水溶性；若診溶性，則該磷源及該鋰源中至少一者 至少一者為火鐵源為非水溶性，則該磷源及該鋰源中 加入去離子⑻將水溶性之㈣、碳源及分散劑 雜化人铷+ #, 之後加入非水溶性之原料以及鋰位置摻 40微来之’以提絲度介於1微米至 〇c之間的溫度及及⑻在介於儀°c至800 =且具有雜置取代或鐵位置取代之概㈣，且該填 换鐵係符合LiaxMlxFebyM2yP〇4/c，其中⑷為裡位置 Jtl素、M2為鐵位置摻雜元素、……工、 為能挑選出較利於後續調聚之磷酸鐘鐵粉末，本發明 ^可現需要包含以下步驟·（F)從製得之_經鐵中選出 粒度介於5微米至20微米之粉末。 此外’本發明之又一主要目的，在於提出一種由前述 製程所製得的磷酸鋰鐵粉束，其不僅具有好調漿之優點， 且由此製成之_子二次電池產品具有高克容量、高倍率 放電性能及循環壽命長等特性。 實施方式】 為充分說明本發明之目的、特徵及功效，使本發明所 201221469 屬技術領域中具有通常知識者能瞭解本發明之内容並可據 以實施，茲藉由下述具體之實施例及實例，對本發明進行 詳細說明如後。 定義 於本文中，用語「包含」、「包括」、「具有」或其任何 變化均旨在涵蓋非排他性之包括。舉例而言，包含一系列 要素的方法、製程、物品或裝置不必然僅限於該等要素， 而是也可包含該方法、製程、物品或裝置未清楚列出或固 有的其他要素。 此外，「或」係指涵蓋性的「或」而非排他性的「或」。 舉例而言，條件「A或B」在下列三種情形均屬滿足：A 為真（或存在）且B為偽（或不存在）、A為偽（或不存在） 且B為真（或存在）以及A、B均為真（或存在）。 於本文中，「一」乃用以描述本發明之要素及組分。此 用法只是為了方便，同時提供本發明一般性的概念，且此 種描述方式應包含一個或至少一個；此外，除非很明顯可 知不含複數，否則單數也應包含複數。 若數量、濃度、尺寸、溫度或其他數值或參數係以範 圍、較佳範圍或一系列上限與下限表示，則其應理解成是 特定揭露由任一對上限或較佳值與下限或較佳值構成之所 有範圍，不論該等範圍是否有分別被揭示。此外，於本文 中若提到數值之範圍時，除非另有說明，否則該範圍應包 括其端點以及範圍内之所有整數與分數。 此外，於本發明中，在可達成發明目的之前提下，數 201221469 值應理解成具有該數字有效位數之精確度。舉例來說 字40應理解成涵蓋從35.〇至44 9之範圍，而數字 應理解成涵蓋從39.50至40.49之範圍。 製程說明 如圖1所示’本發明之鱗酸鐘鐵材料之製造方法 包括以下步驟：原料選擇如、激料配製犯、襞料研磨 SU、造粒SU、煅燒S15;此外，本發明之方法亦可視需 •· I進彳T尺寸選取S16。以下乃就各㈣之細節進行說明， * 錢本領域具有通料識麵了解其时並據以實施。 原料選擇S11 如前所述，本發明之主要精神係使用半化學法來改良 熱碳還原法以製備_鐘鐵，以期材料混合之均句度可以 達到接近化學級混合，而整個匍 又 登個製耘可與固態法一樣簡單 及成本便且。因此’本發明為虛 選擇上係同時使用了固態及=2二#及鐵源f原料之 係以含有三價鐵化合物者為且所使用之鐵源 為水而^原料之選擇主要係根據以下原則：若鐵源 . 為非水H則磷源及鲤源中至少-者為水溶性。換古之， 鱗源、鍾源及鐵源不同時為水溶性，亦不同時為非水雜。 選擇㈣中’鋰之水溶性化合物可選自氮氧化 h 1 5Ll〇H.H2〇)、醋酸鋰（CH3COOLi)、磷酸二 ^ L_4,可同時作為嶙源）、硝酸 化鐘⑽）、棒樣酸鐘⑴心办）或其組合；鐵之水溶 201221469 性化合物可選自硝酸鐵（FeWO3)3)、氣化鐵（FeCl3)或其 組合’·磷之水溶性化合物可選自磷酸（H3p〇4)、磷酸二氫 裡（LiHjO4 ’可同時作為鋰源）、磷酸二氫銨（NH4H2p〇4)、 磷酸氫二銨（（NH4)2HP〇4)、磷酸銨（（NH4)3P〇4)或其組 合。 於原料選擇步驟中，鍾之非水溶性化合物可選自氟化 鋰（LiF)、碳酸鋰（Li2C〇3)、磷化鋰（Lij，可同時作為 碟源）或其組合；鐵之非水溶性化合物可選自三氧化二鐵 (Fe203 )、氫氧化鐵（Fe(0H)3)、磷酸亞鐵（Fe3(pc^， 可同時作為砩源）、鱗酸鐵（Fep〇4 ’可同時作為峨源）或 其組合，磷之非水溶性化合物可選自磷酸鋰（Li3P〇4，可 同時作為鋰源）、磷酸亞鐵（FeKPO4)2,可同時作為鐵源）、 磷酸鐵（FeP〇4，可同時作為鐵源）或其組合。 由上可知，於本發明中，磷源、鐘源及鐵源可分別為 不同之化合物；此外，顧及_可為同—化合物，且鱗 源及鐵源亦可為同一化合物。 於本發明中，構源、鐘源及鐵源之尺寸較佳係為微米 等級，因為較大之尺寸（如毫米等級者）需要耗f較多時 間才能把聚料中的固體粒子粒度研磨至後續製程所需求 者’而較小之尺寸（如奈料級者）則容易因為分子間的 凡得瓦力吸引而造聚的現象，不利於後續製程之 漿料配製S12 在決定好欲使用的鱗源、鐘源及鐵源種類後，即可進 行黎料配製。於此步驟中，先將水溶性之原料、碳源及分 201221469 散劑加入去離子水中，之後再加人非水溶性之原料以及鐘 位置摻雜化合物或鐵位置掺雜化合物，以形成一衆料。 於本發明中，cr % & /、要磷源、鋰源及鐵源不同時為水溶性 或非水溶性化合物’則先加人去離子水中的水溶性之原料 可以疋w’冑源或鐵源，後加人去離子水 之原料也可以是碟源^ 原、鐘源或鐵源’端視製程及產品特性 之需要而定。 於此步驟中，九τ λ山 加入奴源之目的主要在於作為還原劑以 t鍛燒期間使三價鐵還原為二價鐵，同時於鍛燒後可形成 山覆提门產物之導電性。於較佳實施例中，碳源為水 :性；含碳有機化合物，且較佳係選自簾糖、果糖、葡萄 、:：檬酸、聚乙烯吡咯啶酮、環糊精、聚乙烯醇、聚乙 夕油舌旦> 、乃一較佳實施例+，若以產物磷酸鋰鐵 ^里片碳源之添加量係介於2 Wt%至15 wt%之間。 於此步驟中，、 入分散劑之目的主要在於大幅降低水 性I、避:粒:二更可提高非水溶性材料在液體中的分散 y 團聚現象並使整體材料的均勻性提高， 為:離佳的產品。於較佳實施例中，分散劑係 八二： 例如選自聚乙烯型分散劑或多元醇型 ” 於另—較佳實施例中，分散劑係選自十八烷基 本乙烯、山梨醇脂肪酸、失水山梨醇單棕櫚酸酯、聚乙 烯及聚山梨醇、吐溫（Tween)、甘油的單硬脂酸脂。 此外，於本發明之漿料配製過程中，更使用了鋰位置 摻雜化合物或鐵位置摻雜化合物，以藉由其中的裡位置摻 201221469 雜7G素或齡置摻㈣素對產物姐賴之减鐵位置進 行取代’進而提升產物之導電性。 於一較佳實施例中，若以磷酸鋰鐵之鋰含量計，鋰位 置捧雜化合物之添加量係介於0.1 mol%至5 mol%之間，且 裡位置摻雜化合物係選自鈉、鎂、銳、鈦、紀或鑭之氧化 物、碳酸物、氫氧化物、硝酸鹽、有機金屬化合物或氯化 物。 於另一較佳實施例中，若以磷酸鋰鐵之鐵含量計，鐵 位置摻雜化合物之添加量係介於丨m〇1%至15 之間， 且鐵位置摻雜化合物係選自鈣、鋁、鎵、鈦、錘、鎢、釩、 鉻、錳、钴、鎳、銅、鋅、錫或鉍之氧化物、碳酸物、氫 氧化物、确酸鹽、有機金屬化合物或氯化物。 漿料研磨S13 為使產物構酸裡鐵粒子具有較適合後續調漿之尺寸， 同時使磷酸鍾鐵於製成電池之正極時具有較佳的電氣特 性’本發明乃於製程中進行漿料研磨之步驟，以使該漿料 中非水溶性化合物之粒子粒度介於微米至微米之 間。 於一較佳實施例中，漿料研磨步驟係利用研磨機進 行’例如球磨機、攪磨機或珠磨機，且較佳係以球磨機將 漿料中之固體粒子研磨至0. 5微米至6微米之間，或將漿 料中之固體粒子研磨至1. 5微米至2.5微米之間，例如大 約1.6、1.7、1.8、1.9、2.0或2.1微米。將漿料中之固體粒 子研磨至前述大小之目的在於’當產物磷酸鋰鐵粒子被製 12 201221469 成電極時，可提供較為優良的電氣特性。 造粒S14 於漿料研磨完畢後，即可進行造粒，藉由控制造粒步 驟中所使用之進料速度、溫度、壓力或轉速等參數，以產 生粒度介於1微米至50微米之間的前軀體粉末。 於一較佳實施例中，造粒步驟係利用喷霧造粒機進 行，例如一般壓力式、轉盤式或喷流式之喷霧造粒機。於 另一較佳實施例中，造粒步驟係利用喷霧造粒機進行，以 產生粒度介於5微米至20微米之間的球形或類球形前軀體 粉末，例如粒度介於9微米至15微米之間的前軀體粉末。 有別於現有技術中使用的烘乾後再研磨之作法，喷霧造粒 可避免發生原料分層之問題。 藉由控制造粒之條件，可得到尺寸適中的粉末粒子， 不會因為粒子過細而不利調漿，也不會因為粒子過粗而不 利於後續的鋁箔塗覆製程（一般塗覆厚度為例如約100微 米）。 煅燒S15 在將磷源、鋰源、鐵源、碳源和鋰或鐵位置摻雜化合 物製成前軀體粉末後，係於600 °C至800 °C之間的溫度及 還原氣氛下鍛燒該前軀體粉末，以形成碳包覆且具有鋰位 置取代或鐵位置取代之磷酸鋰鐵，且該4酸鋰鐵係符合： Ua-xMlxFeb-yM2yP04/C之化學式，其中Ml為裡位置摻雜 元素、M2為鐵位置摻雜元素、0.9SaSl.l、0$xS0.05、 0.9SbS1.0、0SyS0.15，且 x、y不同時為 0。 13 201221469 一般而言，由於煅燒溫度大約在600 °C至800 °C之 間，所以煅燒後的粉末不會有明顯的收縮現象，且在鍛燒 之後可產生具有橄欖石晶格結構的磷酸鋰鐵。 於一實施例中，煅燒步驟係於氮氣、氬氣、氮氬氣或 氫氬氣所形成的還原氣氛下在窯爐中進行例如1至24小 時。 尺寸選取S16 視製程之需要而，本發明之方法於完成緞燒之後，還 可選擇性的進行尺寸選取，以利挑選出較為適合後續程序 如調漿所需要的磷酸鋰鐵粒子尺寸。 於一實施例中，尺寸選取步驟係以篩網或氣流分級之 方式進行。於一較佳實施例中，係以氣流分級機將煅燒後 的進行粉末分級，以挑選出粒度介於5微米至20微米之磷 酸鋰鐵粉末，其係具有碳包覆且具有鋰位置取代或鐵位置 取代。 實例 為進一步闡述本發明之目的、功效及優點，以下乃搭 配圖式列舉本發明之數個實例說明之，惟應了解的是，該 等實例僅係用以非限制之方式描述本發明，而非用以限制 本發明之範圍，且本發明之範圍應以申請專利範圍所列之 各請求項為準。 實例1 於本實例中，在磷源、鋰源及鐵源化合物中係選取三 氧化二鐵作為非水溶性化合物（鐵源）、磷酸二氳鋰作為水 201221469 溶性化合物（磷源及鋰源）’並以二氧化鈦作為鐵位置摻雜 化合物（以鈦作為置換鐵之摻雜元素）、蔗糖作為碳源。 其中，磷酸二氫鋰係可採用現成的產品或由以下方式 配製：先秤取3.794 kg之碳酸鋰，將其加入2〇 kg之去離 子水中並進行攪拌。在攪拌同時，加入丨丨76 之85%麟 酸，以藉由碳酸鋰與磷酸之反應而生成水溶性的磷酸二氫 鋰及二氧化碳。 於前述之製備方式中，因為是先將粉末態的碳酸鋰加 入水溶液中，之後再加入磷酸，所以即便過程中會產生二 氧化碳，但因此時碳酸鋰粉末係存在於水溶液中，故可以 避免造成碳酸鋰的粉塵飛揚。 接著，在製得的磷酸二氫鋰水溶液中加入〇 26kg之分 散劑FN265及Μ kg之蔬糖並擾掉均句，再加入7 η kg 之三氧化二鐵及0.40 kg之二氧化鈦以形成漿料。繼之，將 混合後之漿料以珠磨機研磨四次，以製作均勻分散且含有 Li、Fe、P、Ti等元素之喊㈣，此時，㈣錢料之 D50約為1,9微米。 ，接著，將上述均勻穩定之漿料以蠕動泵浦送入NB_12 造粒機巾進行粉末造粒驗，以㈣祕體粉末， 其中這粒機之入口溫度係介於21〇至23〇 〇c之間，出口溫 度係介於100至120 °C之間。 最後，將上述前軀體粉末移入還原氣氛之煅燒爐中進 行熱處理，以每分鐘5。(：之速度升溫至72(r(：，並於恆溫 下保持四小時。待爐冷卻後取出產物，並以氣流分級機進 15 201221469 行刀級’筛選出粒徑介於5至20微米的粉末，即可獲得含 鈦之碳包覆磷酸鋰鐵材料。 圖2所不者為實例1所製備之磷酸鋰鐵粉末的X光繞 圖°圖中之結果顯示，此產物具有橄欖石晶格結構且無 雜項峰存在’並顯示鈦原子如預期一樣取代鐵位置。 圖3所示者為此磷酸鋰鐵粉末之SEM照片，由此照片 可見球狀磷酸鐘鐵粉末具有相當均勻之粒徑分佈。 成匕外’為瞭解所製得粉末之特性，可將前述磷酸鋰鐵 材料使祕t池進行測試 。在以鈕扣型電池CR2032進行 '則11式之下’元件〇·2庫侖（C)之放電能力為145.2 mAh/g ; 之放電能力為132.5 mAh/g ; 5C之放電能力為 I 1 ’2mAh/g’此結果顯示元件具有良好之大電流放電能力。 甚—此外，圖4為元件1C充放電之循環壽命結果，由結果 .、、員不兀件在歷經100次循環之電性衰減量係小於15〇/〇。 實例2 實例2與實例1之不同處在於選擇磷酸鐵作為非水溶 生化合物（磷源及鐵源）、氫氧化鋰作為水溶性化合物（鋰 =)、五氧化二鈮作為鋰位置摻雜化合物、抗壞血酸作為碳 办於配製時’先秤取4.34 1^之氫氧化經（1^〇11.2;^2〇；) :、18kg之去離子水中，紐加人之分散劑此p 以及3.17 kg之抗壞血酸。經搜拌後，再加入18 % 2酸鐵及0.336kg之五氧化二銳。接著，如實们一般 仃研磨混合、儒造粒、騎氣氛雜及氣流分級等製 201221469 私以製成含鈮之碳包覆磷酸鋰鐵粉末，其中還 燒之，件係以700 °C燒結16小時。 、 故量測’上述粉末產物之0.2C放電能力為145 i mAh/g ’且1c充放電在歷經100次循環後’其電性衰減旦 係小於0.1〇/〇。 又/里 實例3 實例3與實例1之不同處在於選擇磷酸鋰作為非水溶 性之鐘源及碟源、以硝酸鐵（Fe(N〇3)3 ♦ 9H2Q)作為水溶 性鐵源、硝酸鉻（Cr(N〇3)3 . 9^0)作為鐵位置摻雜化合 物（以二價鉻作為置換鐵之摻雜元素）、葡萄糖作為碳源。 於配製時，先秤取38.574 kg之Fe(N〇3)3 . 9H2〇溶於 16.5 kg之去離子水中，然後加入3.35 kg之葡萄糖及〇 32 kg 之分散劑1221。經攪拌後，再加入3 978 kg之磷酸鋰及2 〇ι kg之Cr(N〇3)3.9H2〇。接著，如實例1 一般進行研磨混合、 喷霧造粒、還原氣氛煅燒及氣流分級等製程，以製成含鉻 之碳包覆磷酸鋰鐵粉末，其中還原氣氛煅燒之條件係以72〇 °C燒結8小時。 經量測，上述粉末產物之02C放電能力為1481 mAh/g ’且1C充放電在歷經_次循環後，電性衰減量小 於 1.8%。 實例4 、實例4與實例！之不同處在於選擇氫氧化鐵作為非水 溶性化合物、以氫氧脑及磷酸相作為水溶性之鐘源與 磷源’並以鑭作為鋰位置之摻雜元素、環糊精作為碳源。 17 201221469 於配製時’先秤取4.366 kg之氩氧化鋰與11 529 k BYK-⑽ 再加入〇,39 kg之分散劑 及3.6 kg之環糊精’最後再加入7,956 kg之氳氧 化鐵及 1,723 kg 之 La(CH3COO)3 · l.5H20。 接著’將形成的漿料利用和實例1相同之方式進行研 磨混合、噴霧造粒、還原氣氛煅燒及氣流分級等製程，以 製成含鑭之碳包覆磷酸鋰鐵材料。 經量測’上述粉末產物之0.2C放電能力為1396 mAh/g ;且1(：充放電在歷經1〇〇次循環後，其電性衰減量 係小於λ〇%。 、 ^ 综言之，本發明係一種製造磷酸鋰鐵材料之方法，其 將全固態混合的熱碳還原法，改為液固共存的半化學法來 混&磷‘鋰鐵的相關原料，並利用固液介面效應及控制固 型物之細微性之方式使漿料中各成分可以達到接近化學法 之混合岣勻度。同時，由於選擇了適當之水溶性原料，製 程中只須進行喷霧造粒即可進行後續之煅繞製程，不必像 化學法—樣需反覆進行清洗即可達高品質之特性，故本方 法可同時擁有固態法之便利性及化學法之均勻性之特點。 此外，在提高磷酸鋰鐵導電度方面，本發明係採同時 添加碳源及鐵或鋰位置取代之方式來提高導電度，且鐵源 化合物是採用具有三價鐵成分的化合物，以符合熱碳還原 法的精神，而碳源部分係採用水溶性有機添加劑，以提高 石反源與其他原料之混合均勻度。同時，為保持產品之均勻 度，本發明採喷霧造粒之方式，以避免一般烘乾製程可能 201221469 產生之原料分層問題。 製程所可能^於本^明之製程中，為避免傳統固液混合 人去離子S的=飛揚現象’乃先將水溶性之原料加 操作性。同時，藉由分散劑的使用= 級::之·、_及鐵源原料可提高 •繼c=::散性’避免粒子發生團聚現象 :㈣酸鐘：而可獲得品質較佳且容易調 之 t’本發明在上文中已以較佳實施例或實例揭露， j錢具有通常知識者應理解的是，料實施例或實例 僅用於描述本發明，而不應解讀為限制本發明之範圍。此 外，應注意的是，舉凡與該等實施例或實例等效之變化與 置換，均應視為涵蓋於本發明之範疇内。因此，本發明 保護範圍當以下文之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1為本發明一較佳實施例之流程示意圖； 圖2為本發明一實例所製得之磷酸鋰鐵粉末的χ光繞射圖； 圖3為本發明-實例所製得之磷酸鐘鐵粉末的sem照片； ，4為本發明一實例所製得之鱗酸鐘鐵粉末於製成電池後 夏測件之1C減電所得之克f容量與壽命關係圖。 【主要元件符號說明】 S11〜S16 方法步騍201221469 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a positive electrode material for a lithium ion secondary battery, and more particularly to a method for producing a lithium iron phosphate (LiFePO4) material and a method for producing the same Lithium iron phosphate powder. [Prior Art] Lithium ion secondary batteries have been widely used in various portable devices due to their high voltage, high energy density, stable discharge voltage, long cycle life, no memory effect and wide operating temperature range. in. In addition, in applications such as high-capacity, high-power electric tools, electric bicycles, and electric vehicles, the development prospects of clock-ion secondary batteries are also quite promising. Among the existing lithium ion secondary battery cathode materials, lithium iron phosphate (or lithium iron phosphate) having an olivine lattice structure has high weight energy density, high charge and discharge life, high charge and discharge capacity, and no toxicity. And low cost and other advantages, it has become the most promising lithium ion secondary battery cathode material. At present, the manufacturing method of lithium iron phosphate can be roughly classified into a solid state method, a hot carbon reduction method, a co-precipitation method, and a hydrothermal method. The solid-state method mainly selects lithium carbonate (Li2C03), ferrous oxalate (FeC204 · 2H20) and ammonium dihydrogen phosphate ((NH4)H2p〇4;) together in the presence of a solvent to mix, dry, and then satin. Because the powder is mixed in a solid state, the uniformity of the raw materials in the solid state process is relatively poor. 201221469 The hot carbon reduction method mainly uses ferric oxide (Fe2〇3) containing ferric iron as an iron source. In such a process, since the raw materials such as bells, irons, and dishes are mixed in a solid state, the hot carbon reduction method has the same disadvantages as the solid-state method, that is, the uniformity of raw material mixing is poor. The co-precipitation method mainly uses ferrous sulfate (FeS〇4), hydrazine hydroxide (LiOH) and phosphoric acid (H3P〇4) as raw materials, and adjusts the pH value of the solution with ammonia water to cause sedimentation of elements such as Li, Fe and P. temple. Although such a process solves the problem of poor mixing uniformity, the process is very complicated because of the need to perform a quality cleaning process through multiple cleaning steps, and there is a problem of wastewater treatment. ^ The hydrothermal synthesis method mainly uses lithium iron phosphate to produce high solubility and reactivity under high pressure and medium temperature conditions, but it is only about 1 〇〇 to 200 because of the low temperature. (:, so the high temperature characteristics of the product are relatively poor. In addition, the hydrothermal synthesis method is also relatively expensive. 乂 In order to improve the shortcomings of the traditional method, various different solid-liquid combined lithium iron phosphate has been proposed in the prior art. For example, S, Chinese Patent Application Publication No. CN101152961 discloses a method for preparing phosphoric acid, the main (four) water-soluble trioxide-iron-stained phosphoric acid two-hour clock, and an oxide of a metal element. Or carbon rhyme, ball-milling in aqueous solution, then spray-drying to obtain a ball-like powder, and then in the _-type powder 2: under-added carbon source, and sequentially into the mash, grinding, first-time calcination, Ball milling, _, second calcination, pulverization, sieving, etc. The method stated in the specification that the method can obtain high-density, excellent bonding 4 201221469 acid-filled bell iron materials, but due to the carbon source needs Adding people twice, the procedure is more troublesome, and the method is to first granulate the powder into powder, then add the carbon source, then carry out the ball milling, the first-time calcination, the ball milling, and the Korean The second two people burned The steps of pulverization, sieving, etc., not only the procedure is cumbersome 'and the spray = after: the spheroidal particles will be broken by the ball milling step, causing the particles of the powder:; method control (from which the irregularly shaped particles can be observed in Figure 1) Therefore, in the process of the subsequent battery process, it is not easy to control the sticking of the slurry and the coating of the electrode material in the process of the subsequent battery process. The Chinese patent application disclosure No. CN1G1355156 discloses; solid-liquid combined preparation The method of phosphoryl iron phosphate, which firstly mixes a bell-source compound, an iron-derived person, a scaly acid, a lanthanum compound, and a small amount of carbon organic precursors: after drying at 80 to 120 γ, ball milling is performed to obtain Body powder, then the precursor powder is purged under an inert atmosphere or a reducing atmosphere, then heated to 400 to 800 〇C, and maintained at a constant temperature for 3 to 8 hours, then cold field, and finally crushed. 乂Because the aforementioned process is The precursor powder is prepared by mixing, drying and re-ball milling the raw materials, so that the produced lithium iron phosphate powder particles are relatively small in winter, and there is a trouble that the subsequent battery process is difficult to adjust the pulp. The process only adds a carbon source to increase the conductivity, and does not add other impurity-removing elements, so the characteristics of the final product are relatively poor. The process disclosed in Chinese Patent Application Laid-Open No. C N101714 65 No. 8 will be salt, metal oxide and The carbon source is added to the aqueous phosphoric acid solution, and a LiHjO4 mixed solution is obtained through the reaction, and then the nano-iron compound is added, ball-milled in a ball mill, spray-dried, and then under inert gas protection in a sintering furnace of 201221469_~qing.c Sintering, and finally washing the acid clock iron powder with water, then at 100~200. (: Drying. Because the iron source of the aforementioned process specifies the use of nano-iron compounds, and the use of push-plate kiln for calcination produces blocky loose phosphoric acid. Lithium iron, so it needs to be broken into particles by a surface processor ^. Accordingly, in addition to limiting the particle size of the iron source material used in this document, the particle size of the satin-fired powder is not easily controlled due to subsequent processing problems. In the paper “The study of solid-liquid junctions” and the preparation of LiFePOVC materials by the one-carb carbothermal reduction method in Guangzhou Chemical Industry Co., Ltd., Volume 39, No. 1, 2011, it also used the method of drying and ball milling in the process, so the output The Wei Zhongtie powder particles are also small and unfavorable, and the properties of the products are relatively poor because the doping elements are not added to improve the conductivity. In view of the fact that various lithium iron phosphate preparation methods known in the prior art are still unsatisfactory, it is necessary to propose a method which is simple in process, inexpensive in manufacturing, and industrially mass-produced, in order to produce a high-gram capacity. , high rate discharge performance and long cycle life products. SUMMARY OF THE INVENTION One of the main objects of the present invention is to provide a method for manufacturing a disk acid iron material which has the advantages of simple process, low manufacturing cost, and industrial mass production compared to other methods in the prior art. Another main object of the present invention is to improve the hot carbon reduction method by a semi-chemical method to prepare lithium iron phosphate, and to achieve the advantage that the entire process is as simple as the solid state process and that the cost is low. The method of the present invention mainly comprises the following steps: (A) selecting the source material of the micron level according to the following rules according to the following rules: if the iron source is the source of the bell, and the iron source containing the ferric compound is not water-soluble; Solubility, wherein at least one of the phosphorus source and the lithium source is water-insoluble, the deionization (8) is added to the phosphorus source and the lithium source, and the water source (four), carbon source and dispersant Hybrid human 铷 + #, after adding water-insoluble raw materials and lithium in the position of 40 micron to 'with a wire thickness between 1 micron and 〇c and (8) at the instrument °c to 800 = And having a hetero-substitution or iron position substitution (4), and the replacement iron system conforms to LiaxMlxFebyM2yP〇4/c, wherein (4) is a Jt element in the inner position, M2 is an iron-site doping element, ... The present invention is advantageous in that it comprises the following steps: (F) selecting a powder having a particle size of from 5 micrometers to 20 micrometers from the prepared iron. In addition, another main object of the present invention is to provide a lithium iron phosphate powder bundle obtained by the foregoing process, which not only has the advantages of good slurry adjustment, but also has a high gram capacity. High rate discharge performance and long cycle life. The present invention is fully described in the technical field of the present invention, which can be understood by those skilled in the art and can be implemented according to the following specific embodiments. EXAMPLES The present invention will be described in detail as follows. DEFINITIONS In this document, the terms "including", "including", "having" or any variations thereof are intended to cover a non-exclusive inclusion. For example, a method, process, article, or device that comprises a plurality of elements is not necessarily limited to the elements, but may also include other elements that are not explicitly listed or possessed by the method, process, article, or device. In addition, "or" means an "or" rather than an exclusive "or". For example, the condition "A or B" is satisfied in the following three cases: A is true (or exists) and B is pseudo (or non-existent), A is pseudo (or non-existent), and B is true (or exists) ) and A and B are true (or exist). In this document, "a" is used to describe the elements and components of the invention. This usage is for convenience only, and is intended to be inclusive of the generality of the invention, and the description should be inclusive of one or at least one. Where the quantity, concentration, size, temperature or other value or parameter is expressed in terms of ranges, preferred ranges or a range of upper and lower limits, it is to be understood as a specific disclosure by any pair of upper or lower and preferred or lower. All ranges of values constitute, whether or not they are disclosed separately. In addition, when a range of values is referred to herein, unless otherwise stated, the range shall include its endpoints and all integers and fractions within the range. Further, in the present invention, before the object of the invention can be attained, the value of 201221469 should be understood as having the accuracy of the number of significant digits. For example, the word 40 should be understood to cover the range from 35. to 44, and the number should be understood to cover the range from 39.50 to 40.49. Process Description As shown in FIG. 1 , the manufacturing method of the scaly ferrite material of the present invention comprises the following steps: raw material selection, excimer preparation, slurry grinding SU, granulation SU, calcination S15; in addition, the method of the present invention Also, if necessary, • I enter the T size and select S16. The following is a description of the details of each (4). * The money field has a common understanding of the time and implementation. Raw material selection S11 As mentioned above, the main spirit of the present invention is to use a semi-chemical method to improve the hot carbon reduction method to prepare _ bell iron, so that the uniformity of the material mixture can be close to the chemical grade mixing, and the entire scorpion is again The crucible can be as simple and cost-effective as the solid state process. Therefore, the present invention is a virtual selection system which uses solid state and =2 two # and iron source f raw materials, and the iron source used is the water and the selection of the raw materials is mainly based on the following Principle: If iron source. For non-aqueous H, at least one of the phosphorus source and the source of water is water soluble. In ancient times, the scale source, the bell source and the iron source are not water-soluble at the same time, and are also non-water mixed at the same time. In (4), the water-soluble compound of lithium may be selected from the group consisting of nitrogen oxide h 1 5Ll〇H.H2〇, lithium acetate (CH3COOLi), phosphoric acid L^4, which can be used as a source of niobium, nitrification clock (10), and a stick. Acid clock (1) heart) or a combination thereof; iron water soluble 201221469 compound can be selected from iron nitrate (FeWO3) 3), gasified iron (FeCl3) or a combination thereof. · Phosphorus water-soluble compound can be selected from phosphoric acid (H3p〇 4), dihydrogen phosphate (LiHjO4 ' can be used as a lithium source), ammonium dihydrogen phosphate (NH4H2p〇4), diammonium hydrogen phosphate ((NH4)2HP〇4), ammonium phosphate ((NH4)3P〇4) Or a combination thereof. In the raw material selection step, the non-water-soluble compound of the bell may be selected from lithium fluoride (LiF), lithium carbonate (Li2C〇3), lithium phosphide (Lij, which can be simultaneously used as a disc source) or a combination thereof; The compound may be selected from the group consisting of ferric oxide (Fe203), iron hydroxide (Fe(0H)3), ferrous phosphate (Fe3 (pc^, which can simultaneously serve as a source of lanthanum), and iron sulphate (Fep〇4' can simultaneously As a source of lanthanum or a combination thereof, the water-insoluble compound of phosphorus may be selected from lithium phosphate (Li3P〇4, which can serve as a lithium source simultaneously), ferrous phosphate (FeKPO4) 2, which can simultaneously serve as an iron source, and iron phosphate (FeP). 〇4, which can be used as an iron source at the same time) or a combination thereof. It can be seen from the above that in the present invention, the phosphorus source, the bell source and the iron source may each be different compounds; furthermore, the _ may be the same compound, and the scale source and the iron source may be the same compound. In the present invention, the size of the source, the source, and the source of iron are preferably in the order of micrometers, because larger sizes (such as millimeters) require more time to grind the solid particles in the aggregate to The requirements of the subsequent processes are smaller, and the smaller size (such as the material grade) is easy to be agglomerated due to the attraction between the molecules. It is not conducive to the preparation of the slurry of the subsequent process. After the source of the scale, the source of the bell and the source of the iron source, the preparation of the material can be carried out. In this step, the water-soluble raw material, the carbon source and the 201221469 powder are added to the deionized water, and then the water-insoluble raw material and the clock-position doping compound or the iron-site doping compound are added to form a mass material. . In the present invention, the Cr% & /, the phosphorus source, the lithium source and the iron source are not water-soluble or water-insoluble compounds at the same time, the first water-soluble raw material in the deionized water can be added to the source or The source of iron source, after adding deionized water, can also be determined by the needs of the dish source, original source, or source of iron source. In this step, the purpose of adding the source of the nine-τ λ mountain is mainly to reduce the ferric iron to divalent iron during the calcination of t as a reducing agent, and at the same time, the electrical conductivity of the product of the mountain coating can be formed after calcination. In a preferred embodiment, the carbon source is water: a carbonaceous organic compound, and is preferably selected from the group consisting of a curtain sugar, a fructose, a grape, a: citric acid, a polyvinylpyrrolidone, a cyclodextrin, a polyvinyl alcohol.聚聚夕油舌> is a preferred embodiment +, if the product lithium iron iron lithium carbon source is added between 2 Wt% and 15 wt%. In this step, the purpose of the dispersant is mainly to greatly reduce the water content I, avoid: particles: two can improve the dispersion of the water-insoluble material in the liquid y agglomeration phenomenon and improve the uniformity of the overall material, as: Good product. In a preferred embodiment, the dispersing agent is 82: for example selected from the group consisting of a polyethylene type dispersing agent or a polyol type. In another preferred embodiment, the dispersing agent is selected from the group consisting of octadecyl present ethylene, sorbitol fatty acid, Liquefied sorbitan monopalmitate, polyethylene and polysorbate, Tween, glycerol monostearate. In addition, in the slurry preparation process of the present invention, a lithium-doped compound is further used. Or the iron is doped with a compound to enhance the conductivity of the product by substituting the 201221469 hetero 7G or the indole (tetracycline) to reduce the conductivity of the product. In a preferred embodiment If the lithium content of lithium iron phosphate is used, the amount of the lithium-based compound is between 0.1 mol% and 5 mol%, and the doping compound is selected from the group consisting of sodium, magnesium, sharp, titanium, and Or an oxide, a carbonate, a hydroxide, a nitrate, an organometallic compound or a chloride. In another preferred embodiment, the amount of the iron-doped compound is added in terms of the iron content of lithium iron phosphate. The system is between 丨m〇1% and 15 The iron-site doping compound is selected from the group consisting of calcium, aluminum, gallium, titanium, hammer, tungsten, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, tin or antimony oxide, carbonic acid, hydroxide, acid Salt, organometallic compound or chloride. Slurry grinding S13 is to make the iron particles in the product acidity have a suitable size for subsequent slurry adjustment, and at the same time, it has better electrical properties when making the bell iron of the battery into the positive electrode of the battery. The invention is a step of slurry grinding in a process such that the particle size of the water-insoluble compound in the slurry is between micrometers and micrometers. In a preferred embodiment, the slurry milling step is performed by a grinder. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Between microns and 2.5 microns, for example about 1.6, 1.7, 1.8, 1.9, 2.0 or 2.1 microns. The purpose of grinding the solid particles in the slurry to the aforementioned size is to 'when the product lithium iron phosphate particles are made into 12 201221469 electrodes Can provide better The electrical properties of the granulation S14 can be granulated after the slurry has been ground. By controlling the parameters such as the feed rate, temperature, pressure or rotation speed used in the granulation step, the particle size is between 1 micron and A precursor powder of between 50 microns. In a preferred embodiment, the granulation step is carried out using a spray granulator, such as a general pressure, rotary or spray type spray granulator. In a preferred embodiment, the granulation step is carried out using a spray granulator to produce a spherical or spheroidal precursor powder having a particle size between 5 microns and 20 microns, for example having a particle size between 9 microns and 15 microns. The precursor powder is different from the drying and re-grinding method used in the prior art, and the spray granulation can avoid the problem of delamination of the raw material. By controlling the granulation conditions, the powder particles of moderate size can be obtained. It is not difficult to adjust the slurry because the particles are too fine, nor is it because the particles are too coarse to facilitate the subsequent aluminum foil coating process (generally, the coating thickness is, for example, about 100 μm). Calcination S15 After calcining the phosphorus source, the lithium source, the iron source, the carbon source, and the lithium or iron-doped compound into a precursor powder, the calcination is carried out at a temperature between 600 ° C and 800 ° C and a reducing atmosphere. a precursor powder, which forms a carbon-coated lithium iron phosphate having a lithium position substitution or an iron position substitution, and the lithium iron acid system conforms to the chemical formula of Ua-xMlxFeb-yM2yP04/C, wherein M1 is a doping element in the middle position M2 is an iron position doping element, 0.9 SaSl.l, 0$xS0.05, 0.9SbS1.0, 0SyS0.15, and x and y are not 0 at the same time. 13 201221469 In general, since the calcination temperature is between 600 ° C and 800 ° C, the calcined powder does not have obvious shrinkage, and after calcination, lithium phosphate having an olivine lattice structure can be produced. iron. In one embodiment, the calcining step is carried out in a furnace under a reducing atmosphere of nitrogen, argon, nitrogen argon or hydrogen argon for, for example, 1 to 24 hours. Size Selection S16 Depending on the process requirements, the method of the present invention can be selectively sized after satin burning to select a lithium iron phosphate particle size that is more suitable for subsequent processes such as slurrying. In one embodiment, the dimensioning step is performed by screen or airflow classification. In a preferred embodiment, the calcined powder is classified by a gas classifier to select a lithium iron phosphate powder having a particle size of 5 to 20 microns, which has a carbon coating and has a lithium position substitution or Replace the iron position. The present invention is further described in the following examples, which are intended to illustrate the invention in a non-limiting manner. It is not intended to limit the scope of the invention, and the scope of the invention should be determined by the claims. Example 1 In this example, in the phosphorus source, the lithium source, and the iron source compound, ferric oxide was selected as the water-insoluble compound (iron source) and lithium diphosphonate as the water 201221469 soluble compound (phosphorus source and lithium source). 'Titanium dioxide is used as an iron-doped compound (titanium as a doping element for replacing iron) and sucrose as a carbon source. Among them, lithium dihydrogen phosphate can be prepared by using ready-made products or by the following methods: 1.749 kg of lithium carbonate is first weighed, and it is added to 2 〇 kg of deionized water and stirred. While stirring, 85% of lanthanum acid of 丨丨76 was added to form water-soluble lithium dihydrogen phosphate and carbon dioxide by reaction of lithium carbonate with phosphoric acid. In the above preparation method, since the lithium carbonate in the powder state is first added to the aqueous solution, and then the phosphoric acid is added, even if carbon dioxide is generated in the process, the lithium carbonate powder is present in the aqueous solution, so that carbonic acid can be avoided. The dust of lithium is flying. Next, in the obtained lithium dihydrogen phosphate aqueous solution, 26 kg of dispersing agent FN265 and Μ kg of vegetable sugar were added and the mean sentence was disturbed, and then 7 η kg of ferric oxide and 0.40 kg of titanium dioxide were added to form a slurry. . Then, the mixed slurry is ground four times in a bead mill to produce a uniform dispersion and contains elements such as Li, Fe, P, Ti, etc. (4), at this time, the D50 of the (4) money material is about 1,9 micrometers. . Then, the above uniformly stabilized slurry is sent to the NB_12 granulator towel by peristaltic pumping for powder granulation test, and (4) the secret body powder, wherein the inlet temperature of the machine is between 21 〇 and 23 〇〇c. The outlet temperature is between 100 and 120 °C. Finally, the above precursor powder was transferred to a calcining furnace of a reducing atmosphere for heat treatment at 5 minutes per minute. (: The speed is raised to 72 (r(:, and kept at constant temperature for four hours. After the furnace is cooled, the product is taken out, and the air classifier is used to enter the 15 201221469 knife grade' to screen out the particle size between 5 and 20 microns. Powder, the titanium-coated carbon-coated lithium iron phosphate material can be obtained. Figure 2 is the X-ray winding of the lithium iron phosphate powder prepared in Example 1. The results in the figure show that the product has an olivine crystal lattice. Structure and no miscellaneous peaks exist 'and show that the titanium atom replaces the iron position as expected. Figure 3 shows the SEM photograph of this lithium iron phosphate powder. From this photograph, it can be seen that the spherical pyrite powder has a fairly uniform particle size distribution. In order to understand the characteristics of the powder produced, the lithium iron phosphate material can be tested in the secret pool. In the button type battery CR2032, the 'component 11' element 〇·2 coulomb (C) The discharge capacity is 145.2 mAh/g; the discharge capacity is 132.5 mAh/g; the discharge capacity of 5C is I 1 '2 mAh/g'. This result shows that the component has a good current discharge capability. Moreover, in addition, Figure 4 shows the component. 1C charge and discharge cycle life results, from the results. The electrical attenuation of the member is less than 15 〇/〇 over 100 cycles. Example 2 The difference between Example 2 and Example 1 is that iron phosphate is selected as the non-aqueous solution (phosphorus source and iron source), hydrogen. Lithium oxide is used as a water-soluble compound (lithium =), antimony pentoxide as a lithium-position doping compound, and ascorbic acid as a carbon in the preparation of 'staining 4.34 1 ^ of hydrogen peroxide (1 ^ 〇 11.2; ^ 2 〇; ): 18kg deionized water, Newgar's dispersant, p and 3.17 kg of ascorbic acid. After mixing, add 18% 2 ferric acid and 0.336kg of pentoxide. Then, as a matter of fact, Grinding and mixing, Confucian granulation, riding atmosphere and airflow classification, etc. 201221469 Privately made carbon-coated lithium iron phosphate powder containing bismuth, which is also burnt, and the parts are sintered at 700 °C for 16 hours. 'The above powder product has a 0.2C discharge capacity of 145 i mAh/g ' and 1c charge and discharge after 100 cycles, its electrical decay is less than 0.1 〇 / 〇. / / Example 3 Example 3 and Example 1 The difference lies in the choice of lithium phosphate as the water-insoluble clock source and dish source, Acid iron (Fe(N〇3)3 ♦ 9H2Q) as a water-soluble iron source, chromium nitrate (Cr(N〇3)3.99^0) as an iron-site doping compound (divalent chromium as a replacement iron) Heterogeneous), glucose as a carbon source. In preparation, weigh 38.574 kg of Fe(N〇3)3. 9H2〇 dissolved in 16.5 kg of deionized water, then add 3.35 kg of glucose and 〇32 kg of dispersion After the stirring, another 3 978 kg of lithium phosphate and 2 〇 1 kg of Cr(N〇3)3.9H2〇 were added. Next, as in Example 1, a process such as grinding and mixing, spray granulation, reduction atmosphere calcination, and gas fractionation is generally performed to prepare a chromium-containing carbon-coated lithium iron phosphate powder, wherein the conditions of calcination in a reducing atmosphere are 72 ° C. Sintered for 8 hours. After measurement, the 02C discharge capacity of the above powder product was 1481 mAh/g' and the electrical attenuation of 1C charge and discharge was less than 1.8% after _ cycles. Example 4, Example 4 and examples! The difference is that iron hydroxide is selected as the non-water-soluble compound, the oxyhydrogen brain and the phosphoric acid phase are used as the water-soluble clock source and the phosphorus source, and ruthenium is used as the doping element of the lithium site and cyclodextrin as the carbon source. 17 201221469 At the time of preparation, 'weigh 4.366 kg of lithium argon oxide and 11 529 k BYK-(10) and then add yttrium, 39 kg of dispersant and 3.6 kg of cyclodextrin. Finally add 7,956 kg of bismuth iron oxide and 1,723 Kg of La(CH3COO)3 · l.5H20. Next, the formed slurry was subjected to a process such as grinding and mixing, spray granulation, reduction atmosphere calcination, and gas flow classification in the same manner as in Example 1 to prepare a carbon-coated lithium iron phosphate material containing ruthenium. After measuring, the 0.2C discharge capacity of the above powder product was 1396 mAh/g; and 1 (the charge and discharge after 1 cycle, the electrical attenuation was less than λ〇%.) ^ In other words, The invention relates to a method for manufacturing a lithium iron phosphate material, which converts the all-solid mixed hot carbon reduction method into a liquid-solid coexisting semi-chemical method to mix & phosphorus-lithium iron related raw materials, and utilizes a solid-liquid interface effect And controlling the fineness of the solids so that the components in the slurry can reach the mixing degree of the chemical method. At the same time, since the appropriate water-soluble raw materials are selected, only the spray granulation can be carried out in the process. The subsequent calcination process does not require high-quality properties like chemical methods, so the method can simultaneously possess the convenience of the solid-state method and the uniformity of the chemical method. In terms of iron conductivity, the present invention adopts a method of simultaneously adding a carbon source and replacing iron or lithium to improve conductivity, and the iron source compound is a compound having a ferric iron component in accordance with the spirit of the thermal carbon reduction method. The carbon source part adopts water-soluble organic additive to improve the mixing uniformity of stone anti-source and other raw materials. Meanwhile, in order to maintain the uniformity of the product, the invention adopts the method of spray granulation to avoid the general drying process possibility 201221469 The stratification of the raw materials produced. The process may be in the process of the present invention, in order to avoid the traditional fly-liquid phenomenon of the deionized S of the solid-liquid mixture, the operation of the water-soluble raw material is first added. At the same time, by the dispersing agent Use = Level::··, _ and iron source raw materials can be improved • Following c=:: dispersive 'avoiding agglomeration of particles: (4) acid clock: and can obtain better quality and easy to adjust t' The present invention has been described with reference to the preferred embodiments or examples, and it should be understood that the present invention is not intended to limit the scope of the present invention. All changes and substitutions that are equivalent to the embodiments or examples are intended to be included within the scope of the present invention. Therefore, the scope of the present invention is defined by the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic flow chart of a preferred embodiment of the present invention; FIG. 2 is a calender diffraction diagram of a lithium iron phosphate powder prepared according to an example of the present invention; The sem photograph of the ferro-phosphorus iron powder; 4 is a graph showing the relationship between the gram-capacity and the lifetime of the scalar pyrite powder prepared in an example of the invention after the battery is fabricated. Component Symbol Description] S11~S16 Method Steps