201246674 六、發明說明： 【發明所屬之技術領域】 本發明係關於—種鋰離子電池用正極活性物質、链離 子電池用正極、及鋰離子電池。 【先前技術】 鐘離子電池之正極活性物質，通常使用含鐘之過渡金 屬氧化物。具體而言，盔 .. ° 為鈷酸鋰（LiCo〇2 )、鎳酸鋰 ⑴响）、錳酸鋰（LiMn2〇4)冑’為了改善特性（高電 容化、循環特性、保存特性、降低内部電阻、比率（_) 特性）或提高安全性’而不斷對該等進行複合化。對於車 輛用或負载調平（l〇adleveling)用等大型用途中之經離子 電池’謀求與至今為止之行動電話用或個人電腦用不同之 特性。 為了改善電池特性’先前使用各種方法，例如於專利 :獻丨中揭示有一種下述鐘二次電池用正極材料之製造方 法，其特徵在於：將 F (〇.8hg.3,〇<g〇.5，M 表示選自由 Co、Mn、 ^ V、Tl、Cu、Ab Ga、Bi、Sn、Zn、Mg、Ge、Nb、 …、3、(^及2"斤組成之群中的至少一 ， “目當於氧欠缺或氧過剩量，表示—〇.1<δ<〇ι)之故 所示的_複合氧化物通過分級機，以平衡分離粒徑 〜m分離絲徑較大者與較小者1重量比為 :Γ法。摻合粒徑較大者與較小者。並且’記載有若根據 以方法’即可輕易製造比率特性與電容各項平衡的鐘二:欠 201246674 電池用正極材料。 [專利文獻1]日本特許第4175026號公報 【發明内容】 專利文獻1中記載之鋰鎳複合氧化物係其組成式中之 氧直過剩者，但即便如此，對於作為高品質之鋰離子電池 用正極活性物質而言，仍然具有改善之餘地。 因此，本發明之課題在於，提供一種具有良好電池特 性之裡離子電池用正極活性物質。 本發月人經努力研究，結果發現正極活性物質之氧量 與電池特性之間存在緊密之相關關係 性物質之氧量為某數值以上時，可獲得特別良好：電= 性。 ，免現正極活性⑯質的碳含量及正極活性物質^ 子表面之殘留驗即碳酸鐘量，與電池特性之間具有密甘 相關關係即，發現當正極活性物質的碳含量在某數崔 下時’又’當正極活性物質的粒子表面之碳酸鐘量在某 值以下時’可得到特別良好的電池特性。 ” 種二Π解為基礎而完成之本發明，於-態樣" 電池^極活性物質，其仙下述組成式表亍 [丨⑽〜yMy) ο”。 成式表不 (上述式中’Μ為選自Sc、Ti、v、Cr、Mn、Fe、c U、ΖΠ、Ga、Ge、八卜 Bi、Sn、Mg、Ca、B 及 z 種以上，，〇<y^〇 7, “ >〇) 戈201246674 6. Technical Field of the Invention The present invention relates to a positive electrode active material for a lithium ion battery, a positive electrode for a chain ion battery, and a lithium ion battery. [Prior Art] A positive electrode active material of a clock ion battery is usually a transition metal oxide containing a bell. Specifically, the helmet: ° is lithium cobaltate (LiCo〇2), lithium nickelate (1), and lithium manganate (LiMn2〇4) 胄' in order to improve characteristics (high capacitance, cycle characteristics, storage characteristics, reduction) The internal resistance, the ratio (_) characteristic) or the improvement of safety' are continuously combined. For ion batteries that are used in large-scale applications such as vehicle use or load leveling, they are different from those used for mobile phones or personal computers. In order to improve the battery characteristics, various methods have been used in the prior art, for example, in the patent: the disclosure discloses a method for producing a positive electrode material for a secondary battery, characterized in that F (〇.8hg.3, 〇<g 〇.5, M represents at least one selected from the group consisting of Co, Mn, ^ V, Tl, Cu, Ab Ga, Bi, Sn, Zn, Mg, Ge, Nb, ..., 3, (^ and 2" First, "the purpose of the oxygen deficiency or oxygen excess, indicating - 〇.1 < δ < 〇 ) 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The weight ratio with the smaller one is: Γ method. The blending particle size is larger and smaller, and 'there is a case where the balance between the ratio characteristic and the capacitance can be easily manufactured according to the method: owing 201246674 In the case of the lithium-nickel composite oxide described in Patent Document 1, the oxygen in the composition formula is excessive, but even in this case, the high-quality material is used as the high-quality material. In the case of a positive electrode active material for a lithium ion battery, there is still room for improvement. An object of the present invention is to provide a positive electrode active material for a ionic battery having good battery characteristics. The present inventors have made an effort to study and found that there is a closely related substance oxygen between the amount of oxygen of the positive electrode active material and the battery characteristics. When the amount is above a certain value, it can be particularly good: electricity = sex. The carbon content of the positive electrode active 16-member and the residual amount of the positive electrode active material, ie, the amount of carbonic acid, have a close relationship with the battery characteristics. The relationship is that it is found that when the carbon content of the positive electrode active material is under a certain number of Cui's, 'when the carbonic acid amount on the surface of the particle of the positive electrode active material is below a certain value, a particularly good battery characteristic can be obtained." The present invention is completed on the basis of the "state" "battery electrode active material, which has the following composition formula [丨(10)~yMy) ο". The formula is not (in the above formula, 'Μ is selected from Sc, Ti, v, Cr, Mn, Fe, c U, ΖΠ, Ga, Ge, 八卜Bi, Sn, Mg, Ca, B, and z or more, 〇<y^〇7, “ >〇 ) Ge
測定之碳量為（MO質量 用LECO 負夏/〇以T，利用中和滴定 4 201246674 子表面的殘留鹼即碳酸鋰量為〇 7〇質量％以下。 本發明之鐘離子電池用正 中，利用m生物質’於-實施形態 中· LEC◦法測定之碳量為G2G質量㈣下利用中 和滴疋所測定之粒子α ^ %以下。 +表面的殘留鹼即碳酸鋰量為0.60質量 於另一實施形 於再另一實施 於再另一實施 本發明之鋰離子電池用正極活性物質 態中，Μ為選自Μη及c〇中之丨種以上。 本發明之鋰離子電池用正極活性物質 形態中’組成式中’ 0： > 0. 〇 5。 本發明之鋰離子電池用正極活性物質 形態中，組成式中，α > 〇. 1。 本發月於另態、樣中為一種經離子電池用正極，其使 用有本發明之鋰離子電池用正極活性物質。 、 本發明於再另—離媒Φ^ L樣中為一種鋰離子電池，立使用有 本發明之鋰離子電池用正極。 、 良好電池特性之鋰離子 根據本發明’可提供一種具有 電池用正極活性物質。 【實施方式】 (鋰離子電池用正極活性物質之構成） 本發明之鋰離子電池用正極活性物質之材料，可廣泛 使用適用作為__般㈣子電池用正極用之正極活性物質的 化合物’尤佳使用銘_(UC002)、鎖酸鐘（LiNi⑹、 錳酸鋰（LiMn2〇4·)等含鋰之過渡金屬氧化物。使用上述材 料而製作之本發明之鋰離子電池用正極活性物質係以下述 201246674 組成式表示：The amount of the carbon to be measured is (the mass of the LECO is negative for the summer, and the amount of the lithium hydroxide is 〇7 〇 mass% or less) by the neutralization titration 4 201246674. m biomass 'in the embodiment', the carbon amount measured by the LEC method is G2G mass (4), and the particle α α % or less measured by the neutralization drip. The residual alkali of the surface, that is, the amount of lithium carbonate is 0.60 mass. In the positive electrode active material state for a lithium ion battery according to still another embodiment of the present invention, the ruthenium is selected from the group consisting of Μη and c〇. The positive electrode active material for a lithium ion battery of the present invention. In the form of the composition formula, 0: > 0. 〇5. In the form of the positive electrode active material for a lithium ion battery of the present invention, α > 〇. 1 in the composition formula. A positive electrode for an ion battery, which uses the positive electrode active material for a lithium ion battery of the present invention. The present invention is a lithium ion battery in a further ion-free Φ^L sample, and the lithium ion battery of the present invention is used. With positive electrode., good battery According to the present invention, a lithium positive electrode active material can be provided as a positive electrode active material for a lithium ion battery. The material of the positive electrode active material for a lithium ion battery of the present invention can be widely used as a material. __ (4) The compound of the positive electrode active material for the positive electrode for the sub-battery is preferably a lithium-containing transition metal oxide such as UC002 or a lock acid clock (LiNi (6) or lithium manganate (LiMn2〇4·). The positive electrode active material for a lithium ion battery of the present invention produced by the above materials is represented by the following 201246674 composition formula:
Ll c LixNi,-x_yMy) 〇2+ α (上述式中，M 為選自 Sc、Ti、v、Cr、Mn、Fe (：()、 CU、&、^、Ge ' A卜 Bi、Sn、Mg、Ca、B 及 Zr 中之 i 種以上，OSxSO·1，〇<y^〇-7，a >〇)。 本發明之鐘離子電池用正極活性物質之氧，於組成式 如上述，係表示為〇2+ a (…），過剩地含有，當用 7離子電池之情形時，電容、㈣特性及電容保持率等 電池特性變得良好。此處，關於a，較佳為a> 為 a > 0.1。 本發明之鍾離子電池用正極活性物質其利用LEC0法 測定2量為〇.則量％以下。LE⑶法係'不溶性氣 :紅外線吸收法，例如於JISR 1603中有所規定。若正極 ::物質的含碳量超過。.4。質量則使用有該正極活性 質的鐘離子電池的電池特性，特以循環特 由LEC〇法測定之碳量，較佳為。.30質量。：; =質量％以下。M於正極材料所含的碳’並非單 子在於正極材料之粒子内部或表面，而是 (Ll2C03)的形式存在。碳酸經為弱驗性，會使電^鍾 降’故殘留驗較少為佳。如上所述，於本發明中，所Γ 極活性物質的含碳量」，係表示於正極材料中以二正 (Ll2C〇3)形態而被含有 馱鋰 質量-乂…則電池特性變得良好此讀少(若為。·4。 本發明之鐘離子電池用正極活性物質，其藉由中和滴 201246674 疋而測定之粒子表面的殘留鹼即碳酸鋰量為〇 7〇質量％以 下。中和滴定係以鹽酸等作為滴定液而使用一般的中和滴 疋法來進行。若粒子表面的殘留鹼即碳酸鋰量超過〇·7質量 %，則重覆進行充放電時與電解液反應， 特性變差。又，若驗較多，則引起氣體產生，：:起電電；： 特性劣化。藉由中和滴定而測定之粒子表面的殘留驗即碳 酸鋰量’較佳為〇.6〇質量％以下，更佳為〇 55質量％以下。 鋰離子電池用正極活性物質係以一次粒子、一次粒子 凝集而形成之二次粒子，或一次粒子及二次粒子的混合物 所構成。鋰離子電池用正極活性物質其一次粒子或二次粒 子的平均粒徑較佳為2〜1 5以m。 若平均粒徑未達2 " m，則變得難以塗布於集電體。若 平均粒徑超過15ym，則於填充時變得容易產生空隙，使填 充性降低。又，平均粒徑更佳為3〜1〇以m。 (鋰離子電池用正極及使用其之鋰離子電池之構成） 本發明之實施形態之鋰離子電池用正極，例如具有下 述構造：將混合上述構成之鋰離子電池用正極活性物質、 導電助劑及黏合劑而製備成之正極合劑，設置於由鋁荡等 而構成之集電體的單面或雙面…本發明之實施形態之 鋰離子電池，具備有上述構成之鋰離子電池用正極。 (鐘離子電池用正極活性物質之製造方法） 其次，詳細說明本發明之實施形態之鋰離子電池用正 極活性物質的製造方法。 首先，製作金屬鹽溶液。該金屬為Ni，及選自Sc、Ti、 201246674 V、Cr、Μη、Fe、广Ll c LixNi, -x_yMy) 〇2+ α (In the above formula, M is selected from the group consisting of Sc, Ti, v, Cr, Mn, Fe (:(), CU, &, ^, Ge ' A Bu Bi, Sn And more than one of Mg, Ca, B, and Zr, OSxSO·1, 〇<y^〇-7, a >〇). The oxygen of the positive electrode active material for the ion battery of the present invention is in the composition formula The above is expressed as 〇2+ a (...), which is excessively contained. When a 7-ion battery is used, battery characteristics such as capacitance, (four) characteristics, and capacitance retention ratio are good. Here, a is preferably a> is a > 0.1. The positive electrode active material for a clock ion battery of the present invention is measured by the LEC0 method and the amount is 2% or less. The LE (3) method is an insoluble gas: an infrared absorption method, for example, in JISR 1603. It is prescribed that the carbon content of the positive electrode:: substance exceeds .4. The mass is the battery characteristic of the clock ion battery having the positive electrode active material, and the amount of carbon measured by the LEC method is preferably used. .30 mass.:; = mass% or less. The carbon contained in the positive electrode material is not in the interior or surface of the particle of the positive electrode material, but in the form of (Ll2C03). The carbonic acid is weakly tested, and it is preferable to reduce the amount of electricity. Therefore, in the present invention, the carbon content of the active material in the present invention is expressed in the positive electrode material. In the case of the second positive (Ll2C〇3) form, the lithium-containing lithium mass-乂 is used, and the battery characteristics are good. This is less. If it is .4, the positive electrode active material for a clock ion battery of the present invention is used. And the amount of lithium carbonate which is the residual alkali on the surface of the particles measured by the drop of 201246674 is 〇7〇 mass% or less. The neutralization titration is carried out by using a normal neutralization drip method using hydrochloric acid or the like as a titration solution. When the amount of the residual alkali, that is, the amount of lithium carbonate exceeds 〇·7 mass%, the reaction with the electrolytic solution is repeated when charging and discharging are repeated, and the characteristics are deteriorated. Further, if a large number of tests are performed, gas is generated, and: the electric power is generated; The residual amount of the surface of the particles measured by the neutralization titration, that is, the amount of lithium carbonate is preferably 〇.6〇 mass% or less, more preferably 〇55 mass% or less. The positive electrode active material for lithium ion batteries is primary particles, once. Secondary particles formed by agglomeration of particles, Or a mixture of primary particles and secondary particles. The positive electrode active material for a lithium ion battery preferably has an average particle diameter of primary particles or secondary particles of 2 to 15 m. If the average particle diameter is less than 2 " m In addition, it becomes difficult to apply to a current collector. When the average particle diameter exceeds 15 μm, voids are likely to occur at the time of filling, and the filling property is lowered. Further, the average particle diameter is more preferably 3 to 1 Torr. The positive electrode for a lithium ion battery according to the embodiment of the present invention has a structure in which a positive electrode active material for a lithium ion battery, a conductive auxiliary agent, and a binder are mixed. The positive electrode mixture prepared by the agent is provided on one side or both sides of the current collector formed by the aluminum slab or the like. The lithium ion battery according to the embodiment of the present invention includes the positive electrode for a lithium ion battery having the above configuration. (Manufacturing Method of Positive Electrode Active Material for Clock Ion Battery) Next, a method for producing a positive electrode active material for a lithium ion battery according to an embodiment of the present invention will be described in detail. First, a metal salt solution is prepared. The metal is Ni, and is selected from the group consisting of Sc, Ti, 201246674 V, Cr, Μη, Fe, and
Ca、B 及“ Wa1，、—、 La、J3 及 Zr 申之 1 錄 LV & 石肖酸鹽' 乙酸越#，+、。又，金屬鹽為硫酸鹽 '氯化物、 ^ 尤佳為硝酸鹽。其原因在於：即便是 以雜質的形態混入燒， 丨：疋 .太* t 成原枓中，亦可直接燒成，故可省去 清洗步驟，•石肖酸鹽會作在备 會作為氧化劑而發揮功能，具有促進燒 成原料中之金屬之氧介^ ^ 月b。預先調整金屬鹽中所含各 金屬成為所欲莫耳比率。蕻 猎此 決疋正極活性物質中之夂 金屬的莫耳比率。 負T之各 其次，使碳酸鋰懸浮於純水，其後投入上述金屬之金 屬鹽溶液而製作金屬碳酸鹽溶液漿料。此時，漿料中會析 出微小粒之含鐘碳酸鹽。又，此時，& 了將碳酸鍾與金屬 鹽溶液混合而進行攪拌，攪拌地愈充分則所生成的衆料粒 子變得愈小，彳更均勻且良好地進行反應，使未反應的碳 酸鐘量減少’藉此可抑制所製作之裡鹽複合體（經離子電 池正極材料用前驅物的碳含量。授拌條件係使用特定 大小的攪拌翼以旋轉數25Orpm左右將溶液攪拌。 再者，於作為金屬鹽之硫酸鹽或氣化物等之熱處理時 其鋰化合物不進行反應之情形時，利用飽和碳酸鋰溶液將 該等之鹽清洗後進行過濾分離。如硝酸鹽或乙酸鹽，其鐘 化合物於熱處理過程中作為鋰原料進行反應之情形時，可 不進行清洗’而直接過濾分離並加以乾燥，藉此使用作為 前驅物。 其次’藉由將經過慮分離之含鋰碳酸鹽加以乾燥，而 獲得鋰鹽之複合體（鋰離子電池正極材料用前驅物）之粉 201246674 末。 成4二埴準/具有特定大小之容量的燒成容器，”燒 成谷器中填充鐘離子電池正 s於錢 次，將填充有鐘離子電池 ：:物之粉末。其 容器搬移至燒成爐，進行燒成。燒^驅物之粉末的燒成 加熱保持特定時間來進行又 成係藉由在氧氣環境下 下進行燒成，則由於會進一步 力壓Ca, B and "Wa1,, -, La, J3 and Zr are reported as 1 LV & sulphate' acetic acid over #, +,. Further, the metal salt is sulfate 'chloride, ^ especially preferably nitric acid Salt. The reason is that even if it is mixed with impurities in the form of impurities, 丨: *. too * t into the original 枓, can also be directly fired, so the cleaning step can be omitted, • oxalate will be prepared It functions as an oxidizing agent and has a function of promoting the oxygen content of the metal in the firing raw material. The metal contained in the metal salt is adjusted in advance to have a desired molar ratio. The molar ratio of the negative T. Next, the lithium carbonate is suspended in pure water, and then the metal salt solution of the metal is introduced to prepare a metal carbonate solution slurry. At this time, the minute particle of the fine particle is precipitated in the slurry. In this case, the carbonated clock and the metal salt solution are mixed and stirred, and the more the stirring is, the smaller the mass particles are formed, and the hydrazine is more uniformly and satisfactorily reacted. The amount of carbonic acid in the reaction is reduced, thereby suppressing the production Salt complex (carbon content of precursor for ion battery positive electrode material. The mixing condition is to stir the solution by using a stirring blade of a specific size at a rotation number of about 25 rpm. Further, it is used as a sulfate or a vapor of a metal salt. In the case where the lithium compound is not reacted during the heat treatment, the salt is washed with a saturated lithium carbonate solution and then subjected to filtration separation, such as a nitrate or an acetate, in which the compound is reacted as a lithium raw material during the heat treatment. It can be directly filtered and separated without drying, and used as a precursor. Secondly, a composite of lithium salts is obtained by drying the lithium-containing carbonate which has been separated by consideration (for lithium ion battery positive electrode materials) Precursor) powder 201246674 at the end. into 4 埴 / / with a specific size of the firing container, "burning the grain filled with plasma ion battery is s in the money, will be filled with the clock ion battery:: the object The powder is transferred to a baking furnace and calcined, and the baking of the powder of the burning material is maintained for a specific time to be further processed. Under firing, due to further beat oxygen atmosphere
然後’自燒成容器取出粉末，使用市售之粉碎=圭 進行粉碎，藉此獲得正極活性物質之粉以I §亥生成微粒的方式來調整^" — 的粉碎強度及粉碎時間而進 “，藉由該粉碎’於將D90設為：累積曲線成 二❶之點的粒子徑（一 ’將⑽設為：累積曲線成為 之點的粒子徑（心）時，可將（D90-Dl0) /2調整 成8^以下。又，更佳為將（D9〇-Dl〇"2調整成6" 以下粉碎性較佳的情形為微粉發生較少，且粗大粉體發 生亦較少’故D90成為相對較小的值，m〇成為相對較大 的值。特別是，在粉碎性裂化之情形時，於粒徑較小的區 域容易變成拉出長摺邊（出現尾巴）《狀態，若成為此情 形’則D10變成相對地小，其結果（d9〇—Dl〇) /2變大。 亦即，（D90—D10) / 2可說是表示粒度不均較少之指標。 於本發明中，藉由抑制上述般粉碎時之微粉的發生， 可減少每體積之粉末的表面積，因此可抑制粒子表面之氫 氧化鋰量。 [實施例] 201246674 以下，提供用以更好地理解本發明及其優點之實施 例’但本發明並不限定於此等實施例。 (實施例1〜1 5 ) 首先，使表1中記載之投入量的碳酸鋰懸浮於純水3.2 公升後’投入4.8公升金屬鹽溶液。此處，金屬鹽溶液係調 整各金屬之硝酸鹽的水合物，使各金屬成為表丨中記載之 組成比，又，調整成使全部金屬莫耳數為u莫耳。攪拌係 藉由具備攪拌翼的攪拌機以旋轉數25〇rpm來進行攪拌。 再者，碳酸鋰之懸浮量為以Li (LixNii x yMy) 〇2“ 表示製品（鋰離子二次電池正極材料，即正極活性物質） 且X為表1之值的量，分別由下式算出者。Then, the powder is taken out from the calcined container, and the powder is pulverized by using a commercially available pulverization method, whereby the powder of the positive electrode active material is obtained by adjusting the pulverization strength and the pulverization time of the powder. By the pulverization, when D90 is set to a particle diameter at which the cumulative curve is two points (a '(10) is set as the particle diameter (heart) at which the cumulative curve becomes a point, (D90-D10) /2 is adjusted to 8^ or less. Also, it is better to adjust (D9〇-Dl〇"2 to 6" The following pulverization is better in the case where the fine powder is less generated and the coarse powder is less generated. D90 becomes a relatively small value, and m 〇 becomes a relatively large value. In particular, in the case of pulverized cracking, it is easy to become a long hem (the tail appears) in a region having a small particle diameter. In this case, D10 becomes relatively small, and the result (d9〇-Dl〇) /2 becomes larger. That is, (D90-D10) / 2 can be said to be an index indicating that the particle size unevenness is small. In the case of suppressing the occurrence of the fine powder during the above pulverization, the powder per volume can be reduced The surface area is such that the amount of lithium hydroxide on the surface of the particles can be suppressed. [Examples] The following examples are provided to better understand the present invention and its advantages. However, the present invention is not limited to the examples. Example 1 to 1 5) First, the lithium carbonate of the input amount shown in Table 1 was suspended in 3.2 liters of pure water, and 4.8 liters of the metal salt solution was put in. Here, the metal salt solution was used to adjust the nitrate hydrate of each metal. Each metal was made into the composition ratio described in the surface, and the total metal molar number was adjusted to be u mole. The stirring was stirred by a stirrer equipped with a stirring blade at a number of revolutions of 25 rpm. The amount of lithium carbonate suspended was expressed by the following formula in which Li (LixNii x yMy) 〇 2 " represents a product (a lithium ion secondary battery positive electrode material, that is, a positive electrode active material) and X is a value of Table 1.
W (g) =73.9χ14χ ( 1 + 0.5 { ( l + x) / ( 1__Χ) } χ A 中’ A」係用以除了作為析出反應必需之量外 預先自懸浮量減去㈣後原料中殘留之碳酸㈣外的们 而乘的數值。「A」，㈣酸鹽或乙酸鹽於心 ==料進行反應之情形時為〇9,如硫酸鹽或氣W 、孤未作為燒成料進行反應之情料為U。 藉由該處理，於溶液令會析出微小粒之 使用«機將該析出物過料離。 技孤 Μ而’將析出物加以乾燥而獲得含鋰碳酸 電池正極材料用前驅物）。 卩鍟離3 器内其^準2成^ ’將含鐘碳酸鹽填充於該燒成溶 八人成容器於大氣壓下放人氧氣環境爐，以 10 201246674 表1中s己載之燒成溫度加妖^ …保持1 〇小時後，進行冷卻，而 獲得氧化物。 其次，使用小型粉碎機（hosokawamicr〇nAcM_2Ec) 將所獲得之氧化物粉碎成特中私 初什现特疋粒徑之微粉為特定的粒度分 布之分布幅度’而蒋得叙雜J2L , 馒付鍟離子二次電池正極材料之粉末。 (實施例1 6 ) 實施例16，係使原料之各金屬為表1所示組成，使金 屬鹽為氣化物，析出含鋰碳酸鹽後，制飽和碳酸鋰溶液 進行清洗、過遽，除此之外，皆進行與實施例卜15相同 之處理。 (實施例17 ) 實施例17，係使原料之各金屬為表丨所示組成，使金 屬鹽為硫酸鹽，使含鋰碳酸鹽析出後，利用飽和碳酸鋰溶 液進行清洗、過濾，除此之外，皆進行與實施例丨〜15相 同之處理。 (實施例1 8 ) 實施例18 ’係使原料之各金屬為表1所示組成，並非 於大氣壓下而是於120KPa之加壓下進行燒成，除此之外， 皆進行與實施例1〜1 5相同之處理。 (比較例1〜3 ) 比較例1〜3，係使原料之各金屬為表1所示組成，且 碳酸鋰與金屬鹽溶液反應時的攪拌條件設為攪拌翼的旋轉 數為150rpm，且對於最後之氧化物的粉碎不進行如實施例 1〜15般之調整，除此之外’皆進行與實施例丨〜15相同之 201246674 處理。 (比較例4〜6 ) 比較例4〜6，係使原料之各金屬為表丨所示組成，且 並非於氧氣環境爐中，而是於空氣環境爐令進行燒成步 驟，除此之外，皆進行與比較例丨相同之處理。 (評價） 一正極材料組成之評價一 各正極材料中之金屬含量係利用感應耦合電漿發射光 譜分析儀（ICP-0ES)測量，而算出各金屬之組成比（莫 耳比）β X ’含氧量係利帛LECO >去測量並算出α。確認 該等結果如表1記載所示。 —採集各正極材料之粉末，藉由雷射繞射型粒度分布測 定裝置（MiCrotrackMT33〇〇EXII)來進行測定平均粒徑。 一碳量之評價一 —正極材料中的碳量係依據JIS G1211、JIS G1215的: 疋’藉由LECO法來進行測定。即，採集G」〜q ^的各 ，材料粉末，且加入2g的不含碳之助燃材料，並放入陶丨 製的掛财後，藉由高周波料爐使其燃燒。利用红外《 檢測器㈣燃燒時的成分並加以定量，藉此求得碳量/ —氫氧化鐘量之評價一 使用鹽酸作為滴定液，藉由中和滴定來測定正極材球 之粒子表面的氫氧化鋰量。 —電池特性之評價— 以85 : 之比例秤畺各正極材料、導電材料與黏合 12 201246674 劑，將黏合劑溶解於有機溶劑（N—甲基吡咯啶酮（N一 methylPyrr〇lid〇ne))後，再將正極材料與導電材料混合於 其中進行漿料化，塗佈於A1箔上加以乾燥後進行壓製而製 成正極。繼而，製作相對電極為Li之評價用2〇32型硬幣電 池（coin cell)，使用 iM— LiPF6 溶解於 EC_ DMC ( i : 1 ) 而成者作為電解液，測量電流密度〇.2C時之放電電容。又， 算出電流密度2C時相對於電流密度〇.2c時之電池電容的 放電電谷之比’獲得比率特性。並且，電容保持率，係藉 由在室溫下將1C之放電電流所獲得之初始放電電容與1〇〇 循環後之放電電容加以比較而測得。 該等之結果示於表1及表2。 13 201246674 粉碎後之（D90 —DIO) /2 (Am) CN v〇 <N vi σ； — rn 寸 VO Os — <5 00 Os — 卜 (S v〇 (Ν 00 os — 00 od ON 00 ν〇 ΟΟ 00 〇 L〇^2j O^lJ A17J | 0.04 I L〇i2J o o ΓΛ Ο d (Ν Ο 1 0.09 1 cn Ο 1 0.07 1 | o.io | (N d 00 o | 0.09 1 L〇^| Ι·*Η Ο ο 1 -0.011 0.00 X o o o o 10.025 I s o o o o o Ο ο Ο ο ο ο o o o o 〇 ο ο ο ο 举賴c | looo | | looo | 1 looo I | looo | o ON o in Os | looo | o (N as o On o 00 ο g ο οο Ο g ο 00 ο 1 ιοοο 1 1000 o os [ιοοο | o cs Os o oo ο ο 00 ο 00 除去Li之全部金屬中之各金屬的組成比 W) i/Ί CN *Ti (Ν < ι/Ί »Λ) £ ΰ «η Ρ tr> fN ΙΛ) (Ν i cn <ri ΓΛ CO m ΓΛ m m ro 一 m 一 ro in <N V"i (N o <^ί m m … m cn cn cn … m »〇 CN o ο *~Η ΓΛ f-i cn ΓΛ 一 ΓΛ m 一 m m «ri ΓΛ m cn in in o 1—^ <Τϊ *η ι/Ί m … m m «ri ΓΛ m m «r； CO in o ο «Ο 2 CO ΓΛ ro ΓΛ … m ΓΛ cn … m … m m § § g m CO ΓΛ c-i m ΓΛ m … m g 碳酸链懸浮量 (g) 1393 1393 1393 1393 1442 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 實施例1 實施例2 |實施例3 1 丨實施例4 i |實施例5 | 實施例6 丨實施例7 | 1實施例81 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 1實施例15 1 |實施例16 1 實施例17 實施例18 比較例1 |比較例2 | 比較例3 比較例4 比較例5 比較例6 寸 201246674 [表2]W (g) = 73.9 χ 14 χ ( 1 + 0.5 { ( l + x ) / ( 1__ Χ ) } ' A ' ' A ' is used to subtract the amount of pre-self-suspended amount (4) in addition to the amount necessary for the precipitation reaction. The value of the carbonic acid (4) is the value of the "A", (4) acid salt or acetate in the case of the heart == material is 〇9, such as sulfate or gas W, or not as a burnt material The situation is U. By this treatment, the solution is used to precipitate the fine particles. The machine is used to separate the precipitates. The technique is used to dry the precipitates to obtain a precursor for the lithium carbonate battery positive electrode material. ).卩鍟 3 3 3 其 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Demon ^ ... After 1 hour, it is cooled to obtain an oxide. Secondly, using a small pulverizer (hosokawamicr〇nAcM_2Ec), the obtained oxide is pulverized into a specific particle size distribution of the micro-powder of the special granules of the special granules, and the distribution range of the specific particle size distribution is obtained by Jiang Dexu J2L, 馒付鍟离子二Powder of secondary battery cathode material. (Example 1 6) In Example 16, the metal of the raw material was a composition shown in Table 1, and the metal salt was vaporized. After the lithium carbonate was precipitated, the saturated lithium carbonate solution was washed and dried. The same processing as in the embodiment 15 was carried out. (Example 17) In Example 17, the metal of the raw material was a composition shown in Table ,, and the metal salt was a sulfate. After the lithium carbonate was precipitated, it was washed with a saturated lithium carbonate solution, and filtered. The same processing as in the embodiment 丨 15 was performed. (Example 1 8) Example 18 'The respective metals of the raw materials were the compositions shown in Table 1, and were not fired under atmospheric pressure but under a pressure of 120 KPa, and were carried out in the same manner as in Example 1 except that ~1 5 the same processing. (Comparative Examples 1 to 3) In Comparative Examples 1 to 3, the respective metals of the raw materials were the compositions shown in Table 1, and the stirring conditions in the reaction between the lithium carbonate and the metal salt solution were such that the number of rotations of the stirring blades was 150 rpm, and The pulverization of the last oxide was not carried out as in the case of Examples 1 to 15, except that the same treatment as in Examples -15 to 15 was carried out in 201246674. (Comparative Examples 4 to 6) In Comparative Examples 4 to 6, the respective metals of the raw materials were made to have the composition shown in Table ,, and were not in an oxygen atmosphere furnace, but were subjected to a firing step in an air atmosphere furnace, and the like. , the same processing as the comparative example. (Evaluation) Evaluation of composition of a positive electrode material The metal content in each positive electrode material was measured by an inductively coupled plasma emission spectrometer (ICP-0ES), and the composition ratio of each metal (Mohr ratio) β X ' was calculated. The oxygen amount is LECO > to measure and calculate α. Confirmation These results are shown in Table 1. - The powder of each positive electrode material was collected, and the average particle diameter was measured by a laser diffraction type particle size distribution measuring device (MiCrotrack MT33(R) EXII). Evaluation of the amount of carbon - The amount of carbon in the positive electrode material was measured by the LECO method in accordance with JIS G1211 and JIS G1215: 疋'. That is, each of the material powders of G" to q^ was collected, and 2 g of the carbon-free combustion-supporting material was added, and it was put into a pottery made by the pottery, and then burned by a high-frequency furnace. Using the infrared "detector (4) combustion component and quantifying it, thereby obtaining the carbon amount / - the evaluation of the amount of hydrogen hydroxide - using hydrochloric acid as the titration solution, the neutralization titration is used to determine the hydrogen on the surface of the particle of the positive electrode ball The amount of lithium oxide. —Evaluation of battery characteristics — The positive electrode material, conductive material and bonding 12 201246674 agent were weighed in a ratio of 85 :, and the binder was dissolved in an organic solvent (N-methylpyrrolidone (N-methylPyrr〇lid〇ne)) Thereafter, the positive electrode material and the conductive material are mixed therein to be slurried, coated on an A1 foil, dried, and pressed to obtain a positive electrode. Then, a coin cell in which a counter electrode was evaluated as a Li 2, 32 type coin cell (coin cell) was used, and iM-LiPF6 was dissolved in EC_DMC (i: 1 ) as an electrolyte solution, and a current density of 2.2C was measured. capacitance. Further, the ratio characteristic was obtained by calculating the ratio of the discharge electric valley of the battery capacity at the current density 2C to the current density C2c. Further, the capacitance retention ratio was measured by comparing the initial discharge capacitance obtained by discharging a current of 1 C at room temperature with the discharge capacitance after 1 Torr. The results of these are shown in Tables 1 and 2. 13 201246674 After smashing (D90 — DIO) /2 (Am) CN v〇<N vi σ; — rn 寸 VO Os — <5 00 Os — 卜 (S v〇(Ν 00 os — 00 od ON 00 〇ΟΟ 00 〇 L〇^2j O^lJ A17J | 0.04 IL〇i2J oo ΓΛ Ο d (Ν Ο 1 0.09 1 cn Ο 1 0.07 1 | o.io | (N d 00 o | 0.09 1 L〇^| Ι·*Η Ο ο 1 -0.011 0.00 X oooo 10.025 I sooooo Ο ο Ο ο ο ο oooo 〇ο ο ο ο 赖 c c | looo | | looo | 1 looo I | looo | o ON o in Os | looo | o (N as o On o 00 ο g ο οο Ο g ο 00 ο 1 ιοοο 1 1000 o os [ιοοο | o cs Os o oo ο ο 00 ο 00 Remove the composition ratio W of each metal in all metals of Li) i/Ί CN *Ti (Ν < ι/Ί »Λ) £ ΰ «η Ρ tr> fN ΙΛ) (Ν i cn <ri ΓΛ CO m ΓΛ mm ro a m a ro in <N V"i (N o <^ί mm ... m cn cn cn ... m »〇CN o ο *~Η ΓΛ fi cn Γ Λ 一ΓΛ m a mm «ri ΓΛ m cn in in o 1—^ <Τϊ *η ι/Ί m ... mm «ri ΓΛ mm «r; CO in o ο «Ο 2 CO ΓΛ ro ΓΛ ... m ΓΛ cn ... m ... mm § § gm CO ΓΛ ci m ΓΛ m ... mg Chain suspension (g) 1393 1393 1393 1393 1442 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 1393 Example 1 Implementation Example 2 | Example 3 1 丨 Example 4 i | Example 5 | Example 6 丨 Example 7 | 1 Example 81 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 1 Example 15 1 |Example 16 1 Example 17 Example 18 Comparative Example 1 | Comparative Example 2 | Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Inch 201246674 [Table 2]
(評價） 實施例1〜18其電池特性皆為良好。3 入，原料之金屬 鹽設為硝酸鹽的實施例1〜15、1 8其電池牲从& 符性特別良好。 進一步，並非於大氣壓力下進行燒成，而是於加壓下進行 燒成的實施例1 8其電池特性為最好。 雖然比較例1〜3其作為原料的金屬之組成與本發明相 同都過度地含有氧，但因為攪拌條件及粉碎條件之原因而 15 201246674 電池特性不良。比較例4〜6其作為原料的金屬之組成在本 發明之範圍以外，進一步因為攪拌條件及粉碎條件之原因 而電池特性不良。 【圖式簡單說明】 無 【主要元件符號說明】 無 16(Evaluation) The battery characteristics of Examples 1 to 18 were all good. 3, the metal of the raw material The salt of the example 1 to 15, the battery of the salt was particularly good. Further, in Example 18, which was not fired under atmospheric pressure but was fired under pressure, the battery characteristics were the best. Although the compositions of the metals as the raw materials of Comparative Examples 1 to 3 were excessively contained in oxygen as in the present invention, they were inferior in battery characteristics due to stirring conditions and pulverization conditions. In Comparative Examples 4 to 6, the composition of the metal as a raw material was outside the range of the present invention, and battery characteristics were further deteriorated due to stirring conditions and pulverization conditions. [Simple diagram description] None [Main component symbol description] None 16