201108493 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種製備具高振實密度撖欖石結構睜極 材料之合成方法，尤指涉及一種可應用在鋰電池產業量產1 特別係指以不同種類高分子為碳源與融鹽法製備鋰離子嵌入 式複合陰極材料之合成方法者。 砍入 【先前技術】 春由綱I酸亞鐵鐘（LiFeP〇4)陰極材料因具備低原料價格、 高安全性、高能量密纽敎電流絲f等優點，就電動車之 能源系統而言，實為-適當材料，近年來已成為鐘離子電也阶 極材料中之後起之秀。惟以近幾年之專财，包含中華民國^ 利第200713672號之磷酸亞鐵鋰晶體材料之製備方法、第 2〇〇61讀號之姻檸檬酸轉_凝膠合成法製備高導電性鱗 酸鋰鹽、以及第Π66744號之磷酸亞鐵鋰、彼贺 為電極材料之應用等’皆大多著重於碳塗佈表 > 材料合成過程中，加入不同種類碳源，其中包含糖類盘有機高 分子’藉以增進粒關之導電度，進而提升電化學性能。缺而， 其所遭遇之瓶駐要有低導電度、低振實密度與健擴散係 數，以及製程中需使用情性氣氛防止二價鐵氧化，造成量產不 便與成本提高等問題’且就目前而言，亦很少有專利提及提升 磷酸亞鐵錄II振實密度之製程技術。故，—般制者係無法 符合使用者於實際使用鋰電池時之高體積能量密度所需。 【發明内容】 201108493 β本發明之主S目的係在於，克服習知技藝所遭遇之上述問 題，並提供-種以不囉類碳源與融鹽法製備雜子嵌入式複 合陰極材料之合成方法。 本發明之次要目的係在於，提供—種可縮短合成材料之假 燒時間，並提高籠讀徑與財蚊，而可在使麟電極時 具有較高體積能量密度之方法者。 本《月之3目的係在於，提供—種可應用在工業量產 2不僅能有效縮減製㈣間與生產成本，同時亦可提升鐘電 池產業於市場應用之競爭力者。 結構陰極發1備勵猶賴石 複合陰極二其=;具圍=石結構之 z!傾 首先，本發明係將一至少含鐘⑹、-至少 二，鹽類㈤一至少含氧酸根（χ〇4)及—至少含高分 子虽碳源（C)之起始物’於 77 固態渡料方式混合均勺开β二體積之有機媒介中，以 於一高溫爐中，在氬氧、〜者將末置 於第-段，I 觀/虱氣或氮氣之混合氣氛中，先 “度進仃第—段假燒熱處理，獲得 式陰極材料，最德脾V複&鐘甘入入 少含融越物質複合鐘嵌入式陰極材料，與一至 處理，即评得度如第二段煆燒熱 體。卩了獲域有祕實錢之複合錢人式陰極材料粉 【實施方式】 係為本發明之製作流程示意圖。 請參閱『第1圖』所示， 201108493 如圖所不.本發鶴—種製備具高振實密度橄欖石結構陰極材 料之合成方法’係藉以不同種類高分子碳源與融鹽製備一具有 橄欖石結構之LixMyX〇4/C複合陰極材料，其中x範圍俾為〇 〇201108493 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for synthesizing a material having a high tap density density of a sapphire structure, in particular, a method for mass production in a lithium battery industry. The synthesis method of lithium ion embedded composite cathode material prepared by using different kinds of polymers as carbon source and molten salt method. Chopped into [previous technology] The spring material of Ligang P. (LiFeP〇4) cathode material has the advantages of low raw material price, high safety, high energy, dense current, current wire f, etc., in terms of the energy system of electric vehicles. In fact, it has become a rising star in the field of electric materials. However, in the past few years, the preparation of high-conductivity sulphate is based on the preparation method of the lithium phosphite crystal material of the Republic of China ^ Lidi 200713672, and the citric acid conversion-gel synthesis method of the second reading. Lithium salts, as well as lithium iron phosphate No. 66744, and applications of electrode materials for Phi's are mostly focused on carbon coating tables. In the synthesis of materials, different types of carbon sources are added, including organic disks of sugar disks. 'In order to improve the conductivity of the grain, and thus improve the electrochemical performance. In short, the bottles encountered have low conductivity, low tap density and good diffusion coefficient, and the use of emotional atmosphere in the process to prevent oxidation of divalent iron, resulting in inconvenient mass production and cost increase. At present, there are few patents mentioning the process technology for improving the tap density of ferrous phosphate II. Therefore, the system cannot meet the high volume energy density required by the user when actually using the lithium battery. SUMMARY OF THE INVENTION 201108493 β The main purpose of the present invention is to overcome the above problems encountered in the prior art, and to provide a synthesis method for preparing hetero-embedded composite cathode materials by using a non-steroidal carbon source and a molten salt method. . A secondary object of the present invention is to provide a method for shortening the smoldering time of a synthetic material and improving the cage reading diameter and the mosquito, while having a higher volume energy density in the lining electrode. The purpose of this month's 3 is to provide a kind of product that can be used in industrial mass production 2 not only to effectively reduce the system (four) and production costs, but also to enhance the competitiveness of the clock battery industry in the market. The structure of the cathode is made up of a composite cathode, which has a sulphide composite; 〇4) and - at least containing the polymer, although the starting material of the carbon source (C) is mixed in the solid medium of the 77 method to open the β two volume of the organic medium, in a high temperature furnace, in argon oxygen, ~ The person will be placed in the first stage, I view / helium or nitrogen mixed atmosphere, first "degree into the first - stage sham burn heat treatment, to obtain the cathode material, the most spleen V complex & The embedded cathode material containing the compound material of the fusion material is treated with the one-to-one treatment, that is, the degree of evaluation is as follows: the second section of the hot-burning body is smashed. The enthalpy of the domain has the secret money of the human-type cathode material powder [embodiment] Schematic diagram of the production process of the invention. Please refer to the "Fig. 1", 201108493 as shown in the figure. The method for synthesizing the olivine-structured cathode material with high-vibration density is based on different types of high-molecular carbon sources. Preparation of a LixMyX〇4/C composite cathode material having an olivine structure, wherein x Wai serve as a billion billion
SxSl.5，y範圍係為o.oigysi 〇，該合成方法並至少包括 下列步驟： (A)混合粉末配製丄丄：將一至少含鋰（Li)、一至少 含金屬鹽類（M)、一至少含氧酸根（χ〇4)及一至少含高分 子當碳源（C)之起始物，於一具適量體積之有機媒介中，以 固態漿料方式混合均勻形成一混合粉末，其中，該至少含鐘之 起始物係可為氫氧化鋰（Lithium Hydroxide，LiOH)、碳酸鋰 (Lithium Carbonate，Li2C03)、磷酸一氫鋰（Lithium hydrogen Phosphate，Li2HK)4)或磷酸二氫鋰（Lithium DihydrogenThe SxSl.5, y range is o.oigysi 〇, and the synthesis method comprises at least the following steps: (A) mixing powder to prepare hydrazine: one containing at least lithium (Li), one containing at least metal salt (M), a mixed powder of at least an oxoester (χ〇4) and a starting material containing at least a polymer as a carbon source (C) in a suitable volume of an organic medium, and uniformly mixed to form a mixed powder, wherein The starting material of the at least clock may be Lithium Hydroxide (LiOH), Lithium Carbonate (Li2C03), Lithium hydrogen Phosphate (Li2HK) 4 or lithium dihydrogen phosphate (Lithium Hydroxide). Lithium Dihydrogen
Phosphate’ )所組成群組中選出之至少一種；該至少含 金屬鹽類之起始物係至少包含一個或多個元素之鈷（c〇)、鐵 (Fe)、錳（Μη)及鎳（Ni)之金屬粉末、碳酸鹽類、硝酸鹽 類、硫酸鹽類、無機鹽類或有機鹽類中選出之至少一種，且上 述含鐵之金屬鹽類係進一步可為鐵粉 '三氧化二鐵（FerricAt least one selected from the group consisting of: Phosphate's at least one metal salt-containing starting material containing at least one or more elements of cobalt (c〇), iron (Fe), manganese (Μη), and nickel ( At least one selected from the group consisting of metal powders, carbonates, nitrates, sulfates, inorganic salts or organic salts of Ni), and the iron-containing metal salt may further be iron powder 'ferric oxide (Ferric
Oxide，Fe2〇3)、氣化亞鐵（Ferrous Chloride, Feck)、草酸亞鐵 (Ferrous 0xalate，Fec204 ·2Η20)硝酸鐵（Ferric 抓加把， Fe(N〇3)3、硫酸亞鐵（Ferrous Sulfate，FeS〇4)或鐵之有機_ 中 選出之至少一種；該至少含氧酸根之起始物係至少含一個或多 個元素之砷（As)、鉬（Mo)、磷（P)、硫（S)、矽（Si)、叙 (V)及鶴（W)中選出之至少一種，且上述含碟酸根之氧酸 根起始物係進一步可為磷酸（PhosphateAcid)、金屬嶙酸鹽、 填酸氫鹽（Hydrogen Phosphate, HPCV2 )或磷酸二氣鹽 201108493 (Dihydrogen Phosphate，H2P〇4 )類中選出之至少一種；該至 少含尚分子當碳源之起始物係可為聚乙二醇（Polyethylene Glycols，PEG )、聚乙烯（Polyethylene, PE )、聚乙烯亞胺 (Polyethylenimine，PEI)、聚丁二酸乙二醇酯（p〇ly-ethylene Succinate, PES)、聚乙二醇單月桂酸醋（p0iyethylene Glycol Mono-Laurate，PEGML)、聚乙二醇二甲醚（p0iyethylene GlycolOxide, Fe2〇3), Ferrous Chloride (Feck), Ferrous Oxalate (Ferrous 0xalate, Fec204 · 2Η20) Ferric nitrate (Ferric grabbing, Fe(N〇3)3, Ferrous sulfate (Ferrous) Sulfate, FeS〇4) or at least one selected from the group consisting of iron; the at least oxyacid starting material is at least one or more elements of arsenic (As), molybdenum (Mo), phosphorus (P), At least one selected from the group consisting of sulfur (S), strontium (Si), Syrian (V), and crane (W), and the above-mentioned acid-containing oxyacid starter system may further be phosphoric acid (PhosphateAcid), metal citrate, At least one selected from the group consisting of Hydrogen Phosphate (HPCV2) or Dihydrogen Phosphate (H2P〇4); the at least one of the starting materials of the carbon source may be polyethylene glycol (Polyethylene Glycols, PEG), Polyethylene (PE), Polyethylenimine (PEI), p〇ly-ethylene Succinate (PES), Polyethylene Glycol Single Laurel P0iyethylene Glycol Mono-Laurate (PEGML), polyethylene glycol dimethyl ether (p0iyethylene Gly) Col
Dimethylether )、聚丙烯（polypr〇pyiene，pp )、聚丁烯 (Polybutene，PB)或聚丙二醇（p〇iypr〇pyiene GiyC〇i，ppG) 所組成群組中選出之至少一種，並且佔產物之重量百分比為5 至95%之間；該有機媒介係可為曱醇（Metiian〇1, CH3〇H)、乙 醇（Ethyl Alcohol，C2H5OH)、丁醇（Butanol，C4H9OH)、異丙 醇（IS〇Pr_ Alcohol，（CH3)2CH〇H )或丙酮（Acetone， CO(CH3)2)中擇其一； (B)第-段恨燒熱處理丄2 :將該混合粉末置於一高溫 爐中’以第-段溫錢行第—段之峨熱處理，以獲得一複合 鋰嵌入式陰極材料；以及 (C )第二段贱熱處理i 3 :將該複合賴人式陰極和 料與一至少含融鹽㈣或共_質進行包覆或混合，並再置灰 該高溫爐中以第二段溫度進行第二段之喊熱處理，以獲料 有南振實密度之複合H嵌人式陰極材料粉體，其中，該融鹽勒 質係可為XC1或XCb之金屬氣化物、奵或犯之金屬細 物、亦或XI或XI2之金屬蛾化物，且該XC1、該XF及該χ 之X 自鋰、鈉⑽、鉀(κ)、铷⑽及鉋⑻奸 組’該XCl2、該ΧΡ2及該邓之χ係選自鎖⑽ 鎂⑽）、mCaM⑻n錄及鐵所構成之群組; 201108493 該共融物質係可為氣化舒·氟化斜（KC⑽）、氣化卸·峨化卸 (KC1-KI)、氣化鉀_硝酸鉀（κα_ΚΝ〇3)、氣化鉀-氫氧化鉀 (KC1-KOH)、氣化鉀·氣化鐘（Kcl_LiC1)或氣化卸敦化鐘 (KCl-LiF)所組成群組選出之至少一種。 ▲、田本發明於運用時，於一較佳實施例中係利用融鹽法以 问分子為碳源，製備鋰離子電池磷酸亞鐵鋰/碳（LiFePO /Γ、 複合陰極材料。首先，係將―至少含链之起始物 至;^ 之起始物、一至少含磷酸根之起始物、以及一至少含高分子之 起始物，於特定體積之有機媒介巾，㈣㈣料方式進行混合 =二至48小時，並於均勻混合後，將所得之混合粉末置於 -面溫爐内，在不同氬氣、統/氫氣或氮氣之混合氣氛中， 先以介於_至4GG°C之間之第—段溫度，持溫假燒i至5 小時進行第-段加齡解，之後再升溫至 i 9⑻。C之間， 持溫煆燒1至24小時以完成第—段煆燒熱處理，並獲得初步 LiFePCVC複合陰極材料。繼之，將該複合陰極材 料與一至少含融鹽物質’如氣化鉀，或是共融物質，再以介於 400至950T之間之第二段溫度，持溫假燒！錢小時進行 第二段瑕燒熱處理，於其巾，係可進—步將此第二段瑕燒熱處 理後之產物以去離子水浸㈣至40分鐘之間，並另以一抽氣 過遽裝置德除水溶液，即可獲得—具有高振實密度之 LiFePOVC陰極材料粉體。 、請參閱『第2圖及第3圖』所示，係分別為本發明以融鹽 法合成LiMWC材料之電池性齡f圖及本發明以融趟法 合成LiFeKVC材料之相關數據比較示意圖。如圖所示^本 發明以融鹽法與不_類高分子為碳源，於755。(：下改變3h、 201108493 2h、lh及〇.5h等不同反應時間合成LiFeP(vc陰極材料並At least one selected from the group consisting of Dimethylether), polypropylene (polypr〇pyiene, pp), polybutene (PB), or polypropylene glycol (p〇iypr〇pyiene GiyC〇i, ppG), and accounts for The weight percentage is between 5 and 95%; the organic medium can be decyl alcohol (Metiian 〇 1, CH 3 〇 H), ethanol (Ethyl Alcohol, C 2 H 5 OH), butanol (Butanol, C 4 H 9 OH), isopropanol (IS 〇 Pr_Alcohol, (CH3)2CH〇H) or acetone (Acetone, CO(CH3)2); (B) first-stage hate heat treatment 丄2: the mixed powder is placed in a high temperature furnace' The first section of the Wen Qianxing section is heat treated to obtain a composite lithium embedded cathode material; and (C) the second section of the tantalum heat treatment i 3 : the composite Lai cathode and the material and at least a molten salt (four) or Co-grinding or mixing, and re-ashing the high-temperature furnace to perform the second-stage shout heat treatment at the second temperature to obtain a composite H-embedded cathode material powder having a south-vibration density, wherein The molten salt chelament may be a metal hydride of XC1 or XCb, a ruthenium or a metal fine substance, or an XI or XI2 Is a moth compound, and the XC1, the XF, and the X of the sputum are from the group consisting of lithium, sodium (10), potassium (κ), strontium (10), and planer (8). The XCl2, the sputum 2, and the scorpion are selected from the group consisting of a lock (10) magnesium. (10)), mCaM (8) n recorded and iron group; 201108493 The co-melting material can be gasification Shu · Fluoride oblique (KC (10)), gasification unloading (KC1-KI), gasification potassium - nitric acid At least one selected from the group consisting of potassium (κα_ΚΝ〇3), potassium carbonate-potassium hydroxide (KC1-KOH), vaporized potassium gasification clock (Kcl_LiC1) or gasification unloading clock (KCl-LiF). ▲When the invention is used, in a preferred embodiment, a lithium ion battery lithium iron phosphate/carbon (LiFePO / Γ, composite cathode material) is prepared by using a salt method to use a molecular salt as a carbon source. First, the system Starting with at least a chain starting material, a starting material containing at least a phosphate, a starting material containing at least a polymer, and a starting material containing at least a polymer, in a specific volume of the organic medium towel, (4) (four) Mixing = 2 to 48 hours, and after uniformly mixing, the resulting mixed powder is placed in a -warm furnace, in a mixed atmosphere of different argon, hydrogen/nitrogen, first between _ to 4GG ° C During the first-stage temperature, hold the temperature for 1 to 5 hours for the first-stage ageing solution, then heat up to i 9 (8). C, hold the temperature for 1 to 24 hours to complete the first-stage heat treatment. And obtaining a preliminary LiFePCVC composite cathode material, and then, the composite cathode material and at least a molten salt substance such as potassium carbonate or a eutectic substance, and then a second temperature between 400 and 950T, Holding a temperature and fever! The second section of the simmering heat treatment is carried out in the hour. Further, the second stage of the heat-treated product is immersed in deionized water for (four) to 40 minutes, and another degassing device is used to remove the aqueous solution, thereby obtaining a LiFePOVC cathode material having a high tap density. Powder, please refer to "Figure 2 and Figure 3" for the comparison of the battery age f map of the LiMWC material synthesized by the melt salt method and the related data of the LiFeKVC material synthesized by the fusion method of the present invention. Schematic. As shown in the figure, the present invention synthesizes LiFeP (vc cathode material) by a salt method and a non-type polymer as a carbon source at 755. (: change 3h, 201108493 2h, lh, and 〇.5h, etc.) and
於〇气充放電速率⑹及2.8至4讀特（v)充放電截止電 壓之環境中進行本發明之電池循環性能測試。由改變油、&、 lh及0.5h等不同反應時間之放電容量循環曲線2 i4， 及各合數據比較中可知，當本發明採用融鹽法時，材料起 始物於高溫炫融態環境下，會有較快之離子擴散速度，使得融 鹽法之起始物反鱗度較—般高溫_法還要快，因此可縮短 合成材料之假燒時間，並提高粉體之粒徑與振實密度，亦 用於電極時可具有較高體積能量密度。 藉^’本侧分子騎源與融餘製備_ 甘入入式複合陰極材料之合成方法’若未來將其應用在工業量 ^，不僅能有效縮減製程時間與生產成本，亦可提升鐘電池 產業於市場應用之競爭力。 ’本發明係一種製備具高振實密度撤視石結構陰 法’可有效改善習用之種種缺點，可縮短合成The battery cycle performance test of the present invention was carried out in the environment of xenon charge and discharge rate (6) and 2.8 to 4 read (v) charge and discharge cutoff voltage. It is known from the comparison of the discharge capacity cycle curve 2 i4 of different reaction times such as oil, &, lh and 0.5h, and the comparison of the respective data. When the present invention adopts the salt-melting method, the material starting material is in a high-temperature and dazzling environment. Underneath, there will be a faster ion diffusion rate, so that the initial sulphate of the molten salt method is faster than the high temperature method, so the smoldering time of the synthetic material can be shortened, and the particle size of the powder can be improved. The tap density, which is also used for electrodes, can have a higher volumetric energy density. By ^' this side of the molecular riding source and the preparation of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Competitiveness in market applications. The present invention is a method for preparing a high-density density-removing stone structure, which can effectively improve various disadvantages of the conventional use and can shorten the synthesis.
燒咖，並提高粉體之練與振雜度，亦可在使用 ;電極㈣有較高體積能量密度，當 ==間r產成本，同時亦可提二產= 更符二用:/而使本發明之産生能更進步、更實用、 提出:物?賴，匈_翻申轉件，綱 此限所^者為本發明之較佳實施例而已，當不能以 义疋土明實施之範圍；故 明說明書内容所作之簡單的等物^發月申明專利耗圍及發 專利涵蓋之範圍内。的等效隻化與修倚，皆應仍屬本發明 201108493 【圖式簡單說明】 第1圖，係為本發明之製作流程示意圖。 第2圖，係本發明以融鹽法合成UFep〇4/c材料之電池性 能示意圖。 第3圖’係本發明以融鹽法合成LiFePCU/C材料之相關數 據比較示意圖。 第4圖，係本發明以融鹽法合成LiFeP〇4/c材料之§ΕΜ 圖。 【主要元件符號說明】 步驟（A)配製混合粉末1 1 步驟（B)第一段煆燒熱處理12 步驟（C)第二段煆燒熱處理13 放電容量循環曲線21〜2 4Burning coffee, and improving the practice and vibration of the powder, can also be used; the electrode (4) has a higher volumetric energy density, when == between the production cost, but also can be used to raise the second production = more suitable for two: / and The invention can be made more progressive, more practical, and proposed: the material is dependent on, the Hungarian _ re-transfer, the limit is the preferred embodiment of the invention, and can not be implemented by Scope; therefore, the simple contents of the contents of the specification are stated in the scope of the patent and the patent coverage. The equivalent and only the reliance should still belong to the present invention. 201108493 [Simplified description of the drawings] Fig. 1 is a schematic diagram of the production process of the present invention. Fig. 2 is a schematic view showing the battery performance of the UFep〇4/c material synthesized by the melt salt method of the present invention. Fig. 3 is a schematic diagram showing the correlation of the data of the LiFePCU/C material synthesized by the melt salt method of the present invention. Figure 4 is a diagram showing the synthesis of LiFeP〇4/c material by the melt salt method of the present invention. [Main component symbol description] Step (A) Preparation of mixed powder 1 1 Step (B) First stage sinter heat treatment 12 Step (C) Second stage sinter heat treatment 13 Discharge capacity cycle curve 21~2 4