200818581 九、發明說明 【發明所屬之技術領域】 本發明係有關一種鋰離子蓄電池用等之非水電解質蓄 電池所使用的正極活性物質、其製造方法、及含有上述正 極活性物質之鋰蓄電池。 【先前技術】 近年來,伴隨手提電腦、手機等之資訊相關機器或通 信機器急速發展,對小型、輕量且具有高能量密度之鋰蓄 電池等之非水電解質蓄電池而言的要求相對提高。非水電 解質蓄電池用正極活性物質,有 LiC〇02、LiNi02、 LiNi0.8Co0.2O2、LiNi1/3C〇i/3Mn1/3〇2、LiMn204 等之鋰與 過渡金屬的複合氧化物,係爲已知。 其中,使用鋰鈷複合氧化物(Li Co 02 )作爲正極活性 物質,使用鋰合金、石墨、碳黑等之碳作爲負極的鋰蓄電 池,由於可得4V級之高電壓,故特別廣泛使用作爲具有 筒能量密度之電池。 另外,集中注目於稱爲鋰鎳鈷(Li-Ni-Co )複合氧化 物、鋰鎳鈷錳(Li-Ni-Co-Mn )複合氧化物之正極活性物 質。此等之正極活性物質,藉由調節鎳、鈷或錳之添加量 ,具有可調節充放電循環特性、速度特性、安全性等之電 池特性的特徵。然而,使用任何的含鋰之複合氧化物的正 極活性物質,皆無法滿足全部的放電容量、充放電循環特 性、速度特性、及充電時之安全性(本說明書中簡稱爲安 -4 - 200818581 全性)之各特性。 爲解決此等問題時,下述之技術係爲已知。例如,提 案使鈷與鈦予以共沉澱時,可得此等之共沉澱物,使該共 沉澱物與碳酸鋰進行混合後,在995°C下燒成所得的含鋰 複合氧化物(參照專利文獻1 )。 另外,提案在經合成的含鋰複合氧化物中浸漬異丙基 三(N-胺基乙基-胺基乙基)鈦酸鹽偶合劑後,在900°C下 進行燒成所得的含鋰複合氧化物(參照專利文獻2)。 此外,提案預先在經合成的含鋰複合氧化物中加入水 與草酸鈦銨後,經由攪拌、噴霧乾燥、解碎、熱處理所得 的在粒子表面上被覆有氧化鈦之含鋰複合氧化物(參照專 利文獻3)。 而且,提案在粒子表面上吸附氫氧化鈦膠體後,在 5 00 °C下進行熱處理所得的含鋰複合氧化物(參照專利文 獻4 ),或在分散有氧化鈦凝膠之丙酮溶液中加入鋰鎳複 合氧化物,予以攪拌、蒸發、乾燥後,在5 0 0 °C下進行熱 處理所得的表面修飾鋰鎳複合氧化物(參照專利文獻5 ) 〇 此外,在Ti(OC2H5)4之乙醇溶液中使含鋰複合氧化 物分散、予以乾燥後,進行熱處理所得的含鋰複合氧化物 (參照專利文獻6、7 )。 專利文獻1 :日本特開2005- 1 23 1 1 1號公報 專利文獻2 :日本特開平4-329267號公報 專利文獻3 :日本特開200 1 -6676號公報 -5- 200818581 專利文獻4:日本特開2002-151078號公報 專利文獻5 :日本特開2004-253305號公報 專利文獻6:日本特開2005-310744號公報 專利文獻7 :日本特開2002-63901號公報 【發明內容】 以上述專利文獻1〜7所得的含鋰複合氧化物粉末, 使用該物作爲蓄電池等之非水電解質蓄電池的正極活性物 質時’於上述各特性中,放電容量及充放電循環特性不充 分,且無法同時充分滿足安全性等之特性,故要求更進一 步經改善者。 此外,鋰蓄電池之負極爲鋰時,一般而言充電電壓爲 4·3 V ’企求提高充電電壓,增加可利用的正極活性物質之 量,以更爲提高放電容量。例如,充電電壓爲4.3 V時正 極活性物質之利用率爲50〜60%,惟充電電壓爲4.5 V時 ,上述利用率約可提高爲70%,更進一步提高放電容量。 上述專利文獻1〜7所得的含鋰複合氧化物,就無法充分 具有充電電壓4.3V時之充放電循環特性而言,在充電電 壓4.5V之高運作電壓下會有充放電循環特性更爲惡化的 情形。 本發明之目的,係提供一種安全性高、於高運作電壓 中具有高放電容量,且充放電循環特性優異的非水電解質 蓄電池用正極活性物質,其製造方法、以及含有該正極活 性物質之鋰蓄電池等的非水電解質蓄電池。 -6 - 200818581 本發明人等再三深入硏究的結果,發現藉由由具有特 定組成之含鋰複合氧化物粒子,在其特定的表面領域中含 有較高特定濃度的鈦之含表面修飾鋰的複合氧化物粒子所 成之正極活性物質,可達成上述之目的。換言之,發現藉 由使用該正極,可達成安全性高、即使以高運作電壓仍具 有高的放電容量、且優異的充放電循環特性。 於本發明中,有關藉由上述含鋰之複合氧化物粒子, 爲何可達成任何優異特性之機構,雖不明確,惟可如下述 予以推測。換言之,於鋰蓄電池等之-非水電解質蓄電池中 ,重複充放電時,在含鋰之複合氧化物粒子與電解液之界 面引起電解液之分解反應,產生含二氧化碳之氣體。然而 ,使用在表面領域中含有較高濃度之鈦的含鋰表面修飾之 複合氧化物粒子時,藉由含鋰之複合氧化物粒子表面上的 活性點與鈦進行反應,可抑制上述電解液之分解反應,可 保持高運作電壓、高體積容暈密度及高的安全性。同時’ 在含鋰之複合氧化物粒子表面層內存在有較高濃度之鈦時 ,可抑制含鋰之複合氧化物粒子中活性成分自電解液溶出 ,結果運作電壓爲4.3V時’即使在4.5V之特高運作電壓 下,可顯著提高充放電循環特性。 此外,上述習知的含鋰之複合氧化物粒子爲含鈦者’ 鈦之含有濃度不大,特別是其表面層之鈦含有量不大。例 如,於上述專利文獻1中記載的含鋰之複合氧化物粒子’ 由於於添加鈦粉末後,在995°C之高溫下進行燒成’故添 加元素進行固溶擴散,爲較粒子內部之粒子表面含有50 200818581 〜100nm範圍之20%以上的鈦者。即專利文獻1中記載的 含鋰之複合氧化物的表面層5nm以內,鈦之原子比例對 元素N而言約高達0.5。而且,元素N係表示含鋰之複合 氧化物粒子中所含的鈷、錳及鎳,專利文獻1之實施例中 係表示銘。 專利文獻2中記載的含鋰之複合氧化物,以鈦偶合劑 使其粒子表面進行化學修飾後,在900°C之高溫下進行熱 處理,該含鋰之複合氧化物的表面層5nm以內,鈦之原 子比例如文獻中所記-載,對元素N而言約高達0.08。 專利文獻3中記載的含鋰之複合氧化物中,在表面層 5 nm以內,鈦之原子比例如文獻中所記載,對元素N而言 約高達0.1 6。 此外,於專利文獻4中使用氫氧化鈦膠體水溶液,於 專利文獻5中使用氧化鈦溶膠之丙酮溶液,在粒子表面使 鈦化合物進行修飾後,在500°C下進行熱處理。使用該溶 膠凝膠法時,不易在粒子表面上以薄薄地、特定比例含有 鈦,含鋰之複合氧化物粒子之表面層5nm以內,鈦之原 子比例對元素N而言約高達0.5。 於專利文獻6與專利文獻7中,使用Ti(OEt)4之乙醇 溶液,在粒子表面上使鈦化合物進行修飾後,惟爲使乙醇 溶液中之Ti(OEt)4的濃度極低時,熱處理後所得的含表面 修飾鋰之複合氧化物的表面層5nm以內,鈦之原子比例 約高達〇 . 5。 因此,本發明係以上述新穎見解爲基準者,具有下述 -8 - 200818581 之要旨。 (1 ) 一種非水電解質蓄電池用正極活性物質,其特 徵爲以一般式LipNxMy02所示含鋰之複合氧化物粒子(其 中,N爲至少一種選自Co、Μη及Ni所成群之元素,Μ ^ 係爲選自除元素Ν以外之過渡金屬、鹼土類金屬及鋁的 _ 元素,0.9gp$l.l、0.9‘x<l.l、0‘yS0.3),在其表面 層上含有鈦,且該表面層5nm以內之鈦含量對元素N而 φ 言、以原子比例爲0.6以上之含表面修飾鋰的複合氧化物 粒子所成。 (2 )如(1 )記載之非水電解質蓄電池用正極活性物 質,其中該含鋰之複合氧化物粒子爲至少一種選自鈷酸鋰 ' 、鎳鈷酸鋰、鎳鈷鋁酸鋰及鎳鈷錳酸鋰所成群之粒子,且 在該含表面修飾鋰之複合氧化物粒子全體中所含的鈦,對 元素N與元素Μ之合計量而言、以原子比例爲〇.〇 00 5〜 0.10。 • ( 3 )如(1 )或(2 )記載之非水電解質蓄電池用正 極活性物質,其中該含表面修飾鋰之複合氧化物粒子具有 5〜25μχη之平均粒徑(D50)。 (4 )如(1 )〜(3 )中任一項記載之非水電解質蓄 電池用正極活性物質,其中該含表面修飾鋰之複合氧化物 粒子在其表面層上含有碳化合物。 (5 )如(4 )記載之非水電解質蓄電池用正極活性物 質,其中該碳化合物爲含碳之鈦配位化合物的部分熱分解 物。 -9- 200818581 (6 ) —種鋰蓄電池,其係爲含有正極與負極與非水 電解液之鋰蓄電池’其特徵爲在該正極係使用如(1)〜 (5 )中任一項記載之正極活性物質。 (7) —種如(1)〜(5)中任一項記載之非水電解 質蓄電池用正極活性物質的製造方法,其特徵爲含有以一 般式LipNxMy〇2所示含鋰之複合氧化物粒子(其中,N爲 至少一種選自Co、Μη及Ni所成群之元素,Μ係爲選自 除元素Ν以外之過渡金屬、鹼土類金屬及鋁的元素’ 〇·9$ρ^1·1、〇·9‘χ<1·1、0SyS0.3)而言,含浸含有鈦 配位化合物之pH値爲1〜1 2的水溶液,再進行混合•乾 燥,製得鈦配位化合物含浸粒子之步驟1,及使以該步驟 1所得的鈦配位化合物含浸粒子在含氧的氣氛環境中進行 熱處理的步驟2。 (8 )如(7 )記載之非水電解質蓄電池用正極活性物 質的製造方法,其中該步驟2之熱處理係在200〜450 °C下 進行。 (9 )如(7 )或(8 )記載之非水電解質蓄電池用正 極活性物質的製造方法,其中該鈦配位化合物爲含碳之鈦 配位化合物。 (1 〇 )如(9 )記載之非水電解質蓄電池用正極活性 物質的製造方法,其中該含碳之鈦配位化合物爲乳酸鈦。 〔發明效果〕 藉由本發明,可提供一種不會降低高安全性、具有高 -10 - 200818581 的運作電壓、高的放電容量、及優異的充放電循環特性的 由含表面修飾鋰之複合氧化物粒子所成的正極活性物質, 該正極活性物質之製造方法,以及使用該正極活性物質之 非水電解質蓄電池。 〔爲實施發明之最佳形態〕 本發明之含表面修飾鋰的複合氧化物粒子,係藉由使 母材之含鋰複合氧化物粒子的表面以鈦化合物進行修飾所 得者。形成母材之含鋰複合氧化物粒子,係以一般式 LipNxMy〇2所示(其中,N爲至少一種選自Co、Μη及Ni 所成群之元素,Μ係爲選自除元素N以外之過渡金屬、 鹼土類金屬及鋁的元素,〇 · 9 ‘ p S 1 · 1、0.9 S X < 1.1、 0^y^0.3 )。於該式中,元素N如上所述,其中以鈷單 獨、鎳單獨、鎳-鈷之組合、鎳-鈷-鋁之組合、鎳-鈷-錳之 組合較佳,另外,就實用性而言以鈷單獨、鎳-鈷-錳之組 合更佳。此外,部分氧(例如〇· 1〜5莫耳% )可以氟原子 取代,以提高電池特性。 此外,式中之P及X以0,較佳者爲0.95SpS1.5 ;0.9$&<1.1,較佳者〇.95‘:^<1.〇5。藉由添加元素]^ ,可更爲提高電池特性。而且,在元素Μ中含有鹼土類 金屬或欽時,y以0之範圍較佳。於含鋰複合氧 化物粒子內部中存在有過多的鈦等之元素時,會使放電容 量降低。元素μ係表示上述之元素,其中較佳者爲選自 A1、Mg、Zr、Ti、Mo、Ca等之2〜4價元素。此外,元 -11 - 200818581 素Μ藉由容量具有性、安全性、充放電循環特性而言, 以至少1種選自Ti、Zr、Mg及Α1所成群者更佳。此時 具體的含鋰複合氧化物之例,如LiNi0.8Co0.HAU.05O2、[Technical Field] The present invention relates to a positive electrode active material used in a nonaqueous electrolyte battery for a lithium ion battery or the like, a method for producing the same, and a lithium secondary battery including the above positive electrode active material. [Prior Art] In recent years, with the rapid development of information-related devices and communication devices such as laptops and mobile phones, there is a relatively high demand for non-aqueous electrolyte batteries such as small, lightweight, lithium-ion batteries having high energy density. The positive electrode active material for a non-aqueous electrolyte battery is a composite oxide of lithium and a transition metal such as LiC〇02, LiNi02, LiNi0.8Co0.2O2, LiNi1/3C〇i/3Mn1/3〇2, and LiMn204. . Among them, a lithium-cobalt composite oxide (Li Co 02 ) is used as a positive electrode active material, and a lithium secondary battery using a carbon such as a lithium alloy, graphite or carbon black as a negative electrode is particularly widely used as a lithium battery having a high voltage of 4 V. Cartridge energy density battery. Further, attention has been focused on a positive electrode active material called a lithium nickel cobalt (Li-Ni-Co) composite oxide or a lithium nickel cobalt manganese (Li-Ni-Co-Mn) composite oxide. These positive electrode active materials are characterized by adjusting the battery characteristics of charge and discharge cycle characteristics, speed characteristics, safety, and the like by adjusting the addition amount of nickel, cobalt or manganese. However, the positive electrode active material using any lithium-containing composite oxide cannot satisfy all of the discharge capacity, charge and discharge cycle characteristics, speed characteristics, and safety during charging (abbreviated as An-4 - 200818581 in this specification) Characteristics of sex). In order to solve such problems, the following techniques are known. For example, when it is proposed to coprecipitate cobalt and titanium, a coprecipitate can be obtained, and the coprecipitate is mixed with lithium carbonate, and then the obtained lithium-containing composite oxide is fired at 995 ° C (refer to the patent). Literature 1). Further, it is proposed to impregnate a lithium-containing composite oxide having a isopropyl tris(N-aminoethyl-aminoethyl) titanate coupling agent, and then calcination at 900 ° C. Composite oxide (refer to Patent Document 2). In addition, it is proposed to add water and a titanium ammonium oxalate to the synthesized lithium-containing composite oxide in advance, and then to form a lithium-containing composite oxide coated with titanium oxide on the surface of the particles by stirring, spray drying, pulverization, and heat treatment (refer to Patent Document 3). Further, it is proposed to adsorb a titanium-containing composite oxide obtained by heat-treating at a temperature of 500 ° C after adsorbing a titanium hydroxide colloid on the surface of a particle (see Patent Document 4), or to add lithium to an acetone solution in which a titanium oxide gel is dispersed. The surface-modified lithium nickel composite oxide obtained by heat-treating the nickel composite oxide after being heated, dried, and dried at 500 ° C (refer to Patent Document 5) 〇 In addition, in an ethanol solution of Ti(OC2H5)4 The lithium-containing composite oxide obtained by dispersing and drying the lithium-containing composite oxide is subjected to heat treatment (see Patent Documents 6 and 7). [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When the lithium-containing composite oxide powder obtained in the documents 1 to 7 is used as a positive electrode active material of a nonaqueous electrolyte secondary battery such as a battery, the discharge capacity and the charge/discharge cycle characteristics are insufficient in the above-described respective characteristics, and it is not sufficient at the same time. To meet the characteristics of safety and the like, it is required to further improve. Further, when the negative electrode of the lithium secondary battery is lithium, in general, the charging voltage is 4·3 V', the charging voltage is increased, and the amount of the positive electrode active material available is increased to further increase the discharge capacity. For example, when the charging voltage is 4.3 V, the utilization rate of the positive active material is 50 to 60%, but when the charging voltage is 4.5 V, the above utilization rate can be increased to about 70%, and the discharge capacity is further increased. The lithium-containing composite oxide obtained in the above Patent Documents 1 to 7 does not sufficiently have a charge-discharge cycle characteristic at a charging voltage of 4.3 V, and the charge-discharge cycle characteristics are deteriorated at a high operating voltage of 4.5 V. The situation. An object of the present invention is to provide a positive electrode active material for a nonaqueous electrolyte battery which has high safety, high discharge capacity, high charge and discharge cycle characteristics, and a method for producing the same, and a lithium containing the positive electrode active material. A non-aqueous electrolyte battery such as a battery. -6 - 200818581 The inventors of the present invention have further intensively studied and found that surface-modified lithium containing a higher specific concentration of titanium in a specific surface region thereof by a lithium-containing composite oxide particle having a specific composition The positive electrode active material formed by the composite oxide particles can achieve the above object. In other words, it has been found that by using the positive electrode, it is possible to achieve high safety, high discharge capacity even at high operating voltage, and excellent charge and discharge cycle characteristics. In the present invention, the mechanism for obtaining any excellent characteristics by the lithium-containing composite oxide particles is not clear, but it can be estimated as follows. In other words, in the non-aqueous electrolyte secondary battery such as a lithium secondary battery, when the charge and discharge are repeated, the decomposition reaction of the electrolytic solution is caused at the interface between the lithium-containing composite oxide particles and the electrolytic solution to generate a gas containing carbon dioxide. However, when a lithium-containing surface-modified composite oxide particle containing a relatively high concentration of titanium in the surface region is used, by reacting the active site on the surface of the lithium-containing composite oxide particle with titanium, the above electrolyte can be suppressed. Decomposition reaction maintains high operating voltage, high volume halo density and high safety. At the same time, when there is a high concentration of titanium in the surface layer of the lithium-containing composite oxide particles, the active component in the lithium-containing composite oxide particles can be inhibited from eluting from the electrolyte, and the operating voltage is 4.3 V even at 4.5. Under the extremely high operating voltage of V, the charge-discharge cycle characteristics can be significantly improved. Further, the above-mentioned conventional lithium-containing composite oxide particles are titanium-containing, and the content of titanium is not large, and in particular, the titanium content of the surface layer is not large. For example, the lithium-containing composite oxide particles described in the above-mentioned Patent Document 1 are calcined at a high temperature of 995 ° C after the addition of the titanium powder. Therefore, the additive element is solid-dissolved and diffused to be a particle inside the particle. The surface contains 50% of titanium in the range of 50 200818581 ~ 100nm. In other words, the surface layer of the lithium-containing composite oxide described in Patent Document 1 is within 5 nm, and the atomic ratio of titanium is as high as about 0.5 for the element N. Further, the element N represents cobalt, manganese and nickel contained in the lithium-containing composite oxide particles, and in the examples of Patent Document 1, it is indicated. The lithium-containing composite oxide described in Patent Document 2 is chemically modified on the surface of the particles by a titanium coupling agent, and then heat-treated at a high temperature of 900 ° C. The surface layer of the lithium-containing composite oxide is within 5 nm. The atomic ratio is, for example, as described in the literature, and is about 0.08 for element N. In the lithium-containing composite oxide described in Patent Document 3, the atomic ratio of titanium is within 5 nm of the surface layer, as described in the literature, and is about 0.16 for the element N. Further, in Patent Document 4, a titanium hydroxide colloidal aqueous solution is used, and in Patent Document 5, an acetone solution of a titanium oxide sol is used, and a titanium compound is modified on the surface of the particles, followed by heat treatment at 500 °C. When the sol gel method is used, it is difficult to contain titanium in a thin and specific ratio on the surface of the particles, and the surface layer of the lithium-containing composite oxide particles is within 5 nm, and the atomic ratio of titanium is as high as about 0.5 for the element N. In Patent Document 6 and Patent Document 7, after the titanium compound is modified on the surface of the particle by using an ethanol solution of Ti(OEt) 4, the heat treatment is performed only when the concentration of Ti(OEt) 4 in the ethanol solution is extremely low. 5。 The surface layer of the surface-modified lithium-containing composite oxide obtained within 5nm, the atomic ratio of titanium is about 〇. Accordingly, the present invention is based on the above novel findings and has the gist of the following -8 - 200818581. (1) A positive electrode active material for a nonaqueous electrolyte secondary battery, characterized by a lithium-containing composite oxide particle represented by a general formula LipNxMy02 (wherein N is at least one element selected from the group consisting of Co, Μη, and Ni, Μ ^ is a _ element selected from the group consisting of a transition metal other than the element lanthanum, an alkaline earth metal, and aluminum, 0.9gp$11, 0.9'x<ll, 0'yS0.3), and contains titanium on the surface layer thereof, and The surface layer has a titanium content of 5 nm or less, and is composed of a composite oxide particle containing surface-modified lithium having an atomic ratio of 0.6 or more. (2) The positive electrode active material for a nonaqueous electrolyte secondary battery according to the above aspect, wherein the lithium-containing composite oxide particles are at least one selected from the group consisting of lithium cobaltate, lithium nickel cobaltate, lithium nickel cobalt aluminate, and nickel cobalt. The particles of the group consisting of lithium manganate and the titanium contained in the entire surface of the composite oxide particles containing the surface-modified lithium, the atomic ratio of the element N and the element Μ is 〇.〇00 5~ 0.10. (3) The positive electrode active material for a nonaqueous electrolyte battery according to (1) or (2), wherein the surface-modified lithium composite oxide particles have an average particle diameter (D50) of 5 to 25 μ? The positive electrode active material for a nonaqueous electrolyte battery according to any one of the above aspects, wherein the surface-modified lithium composite oxide particles contain a carbon compound on the surface layer. (5) The positive electrode active material for a nonaqueous electrolyte secondary battery according to (4), wherein the carbon compound is a partial thermal decomposition product of a carbon-containing titanium complex. -9- 200818581 (6) A lithium secondary battery, which is a lithium secondary battery including a positive electrode and a negative electrode and a non-aqueous electrolyte, wherein the positive electrode system is used in any one of (1) to (5). Positive electrode active material. (7) The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to any one of the aspects of the present invention, characterized in that the lithium-containing composite oxide particles represented by the general formula LipNxMy〇2 are contained. (wherein N is at least one element selected from the group consisting of Co, Μη, and Ni, and the lanthanide is an element selected from transition metals other than element lanthanum, alkaline earth metals, and aluminum' 〇·9$ρ^1·1 〇·9'χ<1·1, 0SyS0.3) is impregnated with an aqueous solution containing a titanium complex having a pH of 1 to 12, and then mixed and dried to obtain a titanium complex impregnated particle. Step 1, and step 2 of subjecting the titanium complex compound impregnated particles obtained in the step 1 to heat treatment in an oxygen-containing atmosphere. (8) The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to (7), wherein the heat treatment in the step 2 is carried out at 200 to 450 °C. (9) The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to the above aspect, wherein the titanium complex compound is a carbon-containing titanium complex. (1) The method for producing a positive electrode active material for a nonaqueous electrolyte secondary battery according to the above aspect, wherein the carbon-containing titanium complex compound is titanium lactate. [Effect of the Invention] According to the present invention, it is possible to provide a composite oxide containing surface-modified lithium which does not have high safety, has an operating voltage of high -10 - 18,815,581, high discharge capacity, and excellent charge and discharge cycle characteristics. A positive electrode active material formed of particles, a method for producing the positive electrode active material, and a nonaqueous electrolyte secondary battery using the positive electrode active material. [Best Mode for Carrying Out the Invention] The surface-modified lithium-containing composite oxide particles of the present invention are obtained by modifying the surface of the lithium-containing composite oxide particles of the base material with a titanium compound. The lithium-containing composite oxide particles forming the base material are represented by the general formula LipNxMy〇2 (wherein N is at least one element selected from the group consisting of Co, Μη, and Ni, and the lanthanide is selected from the group consisting of the element N Elements of transition metals, alkaline earth metals and aluminum, 〇· 9 ' p S 1 · 1, 0.9 SX < 1.1, 0^y^0.3 ). In the formula, the element N is as described above, wherein cobalt alone, nickel alone, a combination of nickel-cobalt, a combination of nickel-cobalt-aluminum, a combination of nickel-cobalt-manganese is preferred, and in terms of practicality A combination of cobalt alone and nickel-cobalt-manganese is preferred. Further, a part of oxygen (e.g., 〇·1 to 5 mol%) may be substituted with a fluorine atom to improve battery characteristics. Further, in the formula, P and X are 0, preferably 0.95SpS1.5; 0.9$&<1.1, preferably 〇.95':^<1.〇5. By adding the element ^^, the battery characteristics can be further improved. Further, when the element cerium contains an alkaline earth metal or a compound, y is preferably in the range of 0. When an excessive amount of an element such as titanium is present in the interior of the lithium-containing composite oxide particles, the amount of discharge is lowered. The element μ represents the above-mentioned element, and preferably a 2 to 4 valent element selected from the group consisting of A1, Mg, Zr, Ti, Mo, Ca, and the like. Further, in the case of capacity, safety, and charge-discharge cycle characteristics, it is more preferable that at least one selected from the group consisting of Ti, Zr, Mg, and Α1 is used. At this time, a specific example of a lithium-containing composite oxide such as LiNi0.8Co0.HAU.05O2
LiNi〇.6Co〇 iMn〇.25Al〇.〇5〇2、LiNii/3C〇i/3Mni/3〇2、LiNi〇 8Co〇.2〇2 、LiNio.4Mno.4Coo.2O2 或 Lii.osfMnojNiojCoo.do wO〗等 - 。亦可使用市售的含鋰複合氧化物。 本發明含表面修飾鋰之複合氧化物粒子,自其粒子表 φ 面5nm以內之表面層上鈦之含有量,對元素N而言、以 原子比例必須爲0.6以上。鈦之含有量在該所定範圍時, 可達成上述本發明之效果。此處,有關自含表面修飾鋰之 複合氧化物粒子之表面5nm以內的表面層上鈦之含有量 ,於本發明中如上所述存在於含表面修飾鋰之複合氧化物 粒子的表面附近之鈦係極爲重要,該粒子之表面層5nm 以內的鈦之含有量,如下所述可藉由XPS分析法(X線 光電子分光法)容易求取。 Φ 而且,於本說明書中,使「自含表面修飾鋰之複合氧 化物粒子表面5nm以內的表面層上,對元素N而言鈦之 原子比例」,簡稱爲「含鋰之複合氧化物粒子表面的原子 比例(Ti/N)」。 ' 本發明中含鋰之複合氧化物粒子表面的原子比例(LiNi〇.6Co〇iMn〇.25Al〇.〇5〇2, LiNii/3C〇i/3Mni/3〇2, LiNi〇8Co〇.2〇2, LiNio.4Mno.4Coo.2O2 or Lii.osfMnojNiojCoo.do wO〗 and so on. A commercially available lithium-containing composite oxide can also be used. In the surface-modified lithium composite oxide particles of the present invention, the content of titanium on the surface layer within 5 nm from the surface of the particle φ is required to be 0.6 or more for the element N. When the content of titanium is within the predetermined range, the effects of the present invention described above can be attained. Here, the content of titanium on the surface layer within 5 nm of the surface of the composite oxide particle containing the surface-modified lithium is as described above in the present invention in the vicinity of the surface of the surface-modified lithium-containing composite oxide particle. It is extremely important that the content of titanium within 5 nm of the surface layer of the particles can be easily determined by XPS analysis (X-ray photoelectron spectroscopy) as follows. Φ In addition, in the present specification, "the atomic ratio of titanium to the element N on the surface layer within 5 nm of the surface of the composite oxide particle containing the surface-modified lithium" is simply referred to as "the surface of the composite oxide particle containing lithium". The atomic ratio (Ti/N)". 'The atomic ratio of the surface of the lithium-containing composite oxide particle in the present invention (
Ti/N)爲0.6以上,較佳者爲0.7以上,更佳者爲0.8以 上,尤佳者爲1.0以上,最佳者爲1·2以上。另外,上限 値沒有特別的限制,原子比例(Ti/N )以1 5以下較佳, 以1 2以下更佳,以1 0以下最佳。 -12- 200818581 於本發明中,含鋰複合氧化物粒子表面之原子比例( Ti/N),藉由XPS分析法(X線光電子分光法)予以分析 。XPS分析法可分析極爲接近粒子表面之層中所含的元素 種類或元素之存在比例。而且,XPS分析裝置之例,如 PHI公司製ESCA5400 (無單色型)。另外,於本發明中 可以高感度檢測,且以儘可能使用其他元素之波峰與沒有 重複的波峰較佳。具體而言,分析鈦時以計算感度高的 2p之波峰所使用者較佳。此外,分析鈷、錳或鎳時,以 使用計算感度高的2p3之波峰者較佳。 另外,粉末表面之元素分析中,各使用的ΕΡΜΑ ( X 線微分析器)分析或EDS (能量分散型X線分光法)分 析,係爲可得有關自粒子表面至表面層50〜100nm之較 深範圍的元素之資訊的分析法。因此,以測定本發明含鋰 複合氧化物之粒子表面的原子比例(Ti/N )時,不爲企求 〇 本發明含表面修飾鋰之複合氧化物粒子中所含的鈦, 爲粒子全體時,對元素N與元素Μ之合計量而言,原子 比例以0.0005〜0.10較佳,以0.0008〜0.08更佳。 元素Μ中含有鈦時,在含表面修飾鋰之複合氧化物 粒子全體中所含的鈦,對元素Ν與元素Μ之合計量而言 ,以原子比例爲〇 . 〇 1〜〇 · 〇 8較佳。此外,元素Μ不含鈦 時,含表面修飾鋰之複合氧化物粒子全體中所含的鈦,對 元素Ν與元素Μ之合計量而言,以原子比例爲〇·〇〇〇8〜 0.03更佳。 -13- 200818581 而且,表面層上亦可含有鈦以外之元素。鈦以外之元 素存在於表面層時,較佳的元素例如鎂。 另外,本發明之含表面修飾的複合氧化物粒子,以在 表面層上另含有碳化合物。該碳化合物以至少具有具碳-氧雙鍵構造之含碳的鈦配位化合物之部分熱分解物較佳。 其中,碳-氧雙鍵以碳酸鹽基、羰基更佳。具體的化合物 ,以至少含有一種選自檸檬酸欽、酒石酸鈦、草酸欽、丙 二酸鈦、馬來酸鈦、蘋果酸鈦、蔔萄酸鈦、乳酸鈦及乙醛 酸鈦之化合物的部分熱分解物較佳。其中,以乳酸鈦之部 分熱分解物更佳。而且,於本說明書中,部分熱分解物係 指具有碳-氧雙鍵構造,且使部分含表面修飾鋰之複合氧 化物粒子表面上存在有鈦配位化合物進行熱分解者。 第1圖係爲以例2或例4所合成的含鋰複合氧化物之 紅外線吸收(IR )光譜圖。以例2所合成的含表面修飾鋰 之複合氧化物的IR光譜,係在1300〜1700CHT1之範圍有 強的吸收波峰。該吸收波峰係爲來自碳··氧雙鍵之吸收波 峰,係表示在表面層上存在有碳化合物。此外,該碳化合 物係表示作爲原料所使用的含碳之鈦配位化合物的部分熱 分解物。另外,以例4所合成的含鋰之複合氧化物的IR 光譜中,沒有來自上述碳-氧雙鍵之強的吸收波峰。 而且,第2圖係爲測定在使乳酸鈦進行乾燥的粉末( 乾燥粉)中施加熱時之重量變化(TG及DTG)與發熱量 之變化(DTA )者。藉由第2圖可知,使乳酸鈦乾燥粉加 熱至20 0〜45 0 °C範圍時,該乾燥粉之重量急劇減少,且伴 -14- 200818581 隨有激烈的發熱反應。換言之,示唆有於該溫度範圍內, 乳酸鈦會引起部分熱分解,且放出二氧化碳等之氣體,進 行脫碳酸反應。另外,可知在450°C以上時,幾乎完成熱 分解反應。示唆在該階段中,鈦配位化合物轉化成氧化鈦 或氫氧化鈦。 由此等可知,於例2中藉由在3 5 0°C下進行熱處理所 合成的含表面修飾鋰之複合氧化物粒子的表面層中,存在 有具碳-氧雙鍵之鈦化合物,在表面層上存在有碳化合物 ,且該碳化合物係爲作爲原料所使用的含碳之鈦配位化合 物的部分熱分解物。藉此可提高充放電循環特性,惟對於 有關更爲提高充放電循環特性的理由及其機構皆不明確。 本發明之含表面修飾鋰之複合氧化物粒子,對預先合 成的LiNi1/3C〇1/3Mn1/302等之含鋰複合氧化物而言,含浸 含鈦配位化合物之pH値爲1〜1 2之水溶液(於本說明書 中稱該水溶液爲Ti水溶液),再進行混合•乾燥,藉由 進行熱處理製得。而且,其中Ti水溶液之pH値以1〜8 較佳。 作爲Ti水溶液之原料的鈦化合物,沒有特別的限制 ,惟就可提高表面修飾所使用的含鈦之水溶液中存在的鈦 之溶解性而言,以鈦之配位化合物較佳。此外,該鈦之配 位化合物溶解於水中時,係指配位於鈦上形成配位化合物 之化合物。另外,進行加熱處理後,爲在含表面修飾鋰之 複合氧化物粒子表面上可殘存企求的上述之碳化合物時, 鈦化合物以含碳之鈦配位化合物較佳,以具有羰基或碳酸 -15- 200818581 基之含碳的鈦配位化合物更佳,以具有羰基或碳酸基之有 機酸鈦配位化合物最佳。具體而言,鈦化合物以至少一種 選自檸檬酸鈦、酒石酸鈦、草酸鈦、丙二酸鈦、馬來酸鈦 、蘋果酸鈦、葡萄酸鈦、乳酸鈦及釔醛酸鈦較佳。其中, 鈦化合物以乳酸鈦更佳。該碳之存在,以具有可更爲提高 含表面修飾鋰之複合氧化物的充放電循環特性之傾向較佳 〇 此外,上述Ti水溶液亦可含有羧酸。在Ti水溶液中 含有羧酸時,上述之羧酸就對水溶液之溶解度而言,以碳 數2〜8之羧酸較佳,其中以至少一種選自檸檬酸、酒石 酸、草酸、丙二.酸、馬來酸、蘋果酸、葡萄酸、乳酸及乙 醛酸鈦更佳。Ti水溶液中羧酸之含量以〇 · 〇 5〜3 0重量% 較佳,以〇· 1〜20重量%更佳。在Ti水溶液中含有羧酸時 ,可提高Ti水溶液中所含的鈦配位化合物對水之溶解性 ,且具有不易使Ti水溶液中溶解的鈦配位化合物另外析 出的傾向。Ti/N) is 0.6 or more, preferably 0.7 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more, and most preferably 1.2 or more. Further, the upper limit 値 is not particularly limited, and the atomic ratio (Ti/N) is preferably 15 or less, more preferably 1 2 or less, and most preferably 10 or less. -12- 200818581 In the present invention, the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles is analyzed by XPS analysis (X-ray photoelectron spectroscopy). The XPS analysis analyzes the proportion of elements or elements contained in layers that are very close to the particle surface. Further, an example of an XPS analyzer is an ESCA 5400 (no monochromatic type) manufactured by PHI Corporation. Further, in the present invention, high sensitivity detection can be performed, and it is preferable to use peaks of other elements as much as possible and peaks which are not repeated. Specifically, it is preferable to use a 2p peak having a high sensitivity when analyzing titanium. Further, when analyzing cobalt, manganese or nickel, it is preferred to use a peak of 2p3 which is highly sensitive. In addition, in the elemental analysis of the powder surface, each of the ΕΡΜΑ (X-ray microanalyzer) analysis or EDS (energy dispersive X-ray spectroscopy) analysis is used to obtain a correlation from the surface of the particle to the surface layer of 50 to 100 nm. An analysis of the information of elements in the deep range. Therefore, when the atomic ratio (Ti/N) of the surface of the particle of the lithium-containing composite oxide of the present invention is measured, the titanium contained in the composite oxide particle containing the surface-modified lithium of the present invention is not required. For the total amount of the element N and the element Μ, the atomic ratio is preferably 0.0005 to 0.10, more preferably 0.0008 to 0.08. When titanium is contained in the elemental yttrium, the titanium contained in the entire composite oxide particles containing the surface-modified lithium has an atomic ratio of Ν. 〇1 〇 〇 〇8 in terms of the total amount of the element Ν and the element Μ. good. In addition, when the element Μ does not contain titanium, the titanium contained in the entire composite oxide particles containing the surface-modified lithium is more preferably 原子·〇〇〇8 to 0.03 in terms of the atomic ratio of the element Ν and the element Μ. good. -13- 200818581 Moreover, the surface layer may also contain elements other than titanium. When an element other than titanium is present in the surface layer, a preferred element such as magnesium. Further, the surface-modified composite oxide particles of the present invention further contain a carbon compound on the surface layer. The carbon compound is preferably a partial thermal decomposition product of a carbon-containing titanium complex having at least a carbon-oxygen double bond structure. Among them, the carbon-oxygen double bond is more preferably a carbonate group or a carbonyl group. a specific compound containing at least one selected from the group consisting of citric acid, titanium tartrate, oxalic acid, titanium malonate, titanium maleate, titanium malate, titanium hydride, titanium lactate, and titanium glyoxylate. Thermal decomposition products are preferred. Among them, the thermal decomposition product is more preferably a part of titanium lactate. Further, in the present specification, the partial thermal decomposition product means a structure having a carbon-oxygen double bond structure and thermally decomposing a titanium complex compound on the surface of the composite oxide particles partially containing surface-modified lithium. Fig. 1 is an infrared absorption (IR) spectrum of the lithium-containing composite oxide synthesized in Example 2 or Example 4. The IR spectrum of the surface-modified lithium-containing composite oxide synthesized in Example 2 had a strong absorption peak in the range of 1300 to 1700 CHT1. The absorption peak is an absorption peak derived from a carbon-oxygen double bond, and indicates that a carbon compound exists on the surface layer. Further, the carbon compound means a partial thermal decomposition product of a carbon-containing titanium complex used as a raw material. Further, in the IR spectrum of the lithium-containing composite oxide synthesized in Example 4, there was no strong absorption peak derived from the above carbon-oxygen double bond. In addition, the second figure is a measure of the change in weight (TG and DTG) and the change in calorific value (DTA) when heat is applied to the powder (dry powder) in which titanium lactate is dried. As can be seen from Fig. 2, when the dry powder of titanium lactate is heated to a range of 20 0 to 45 ° C, the weight of the dry powder is drastically reduced, and the intense heat reaction is accompanied by -14-200818581. In other words, in the temperature range, the titanium lactate causes partial thermal decomposition, and a gas such as carbon dioxide is released to carry out a decarbonation reaction. Further, it is understood that the thermal decomposition reaction is almost completed at 450 °C or higher. In this stage, the titanium coordination compound is converted into titanium oxide or titanium hydroxide. Thus, it can be seen that in the surface layer of the surface-modified lithium-containing composite oxide particles synthesized by heat treatment at 350 ° C in Example 2, a titanium compound having a carbon-oxygen double bond is present. A carbon compound is present on the surface layer, and the carbon compound is a partial thermal decomposition product of the carbon-containing titanium complex compound used as a raw material. Thereby, the charge-discharge cycle characteristics can be improved, but the reason and mechanism for further improving the charge-discharge cycle characteristics are not clear. The surface-modified lithium-containing composite oxide particles of the present invention have a pH 含 of 1 to 1 2 for impregnating the titanium-containing complex compound with respect to the lithium-containing composite oxide such as LiNi1/3C〇1/3Mn1/302 synthesized in advance. The aqueous solution (referred to as the aqueous solution of Ti in the present specification) is mixed and dried, and is obtained by heat treatment. Further, it is preferable that the pH of the Ti aqueous solution is 1 to 8. The titanium compound which is a raw material of the Ti aqueous solution is not particularly limited. However, in terms of improving the solubility of titanium present in the titanium-containing aqueous solution used for surface modification, a coordination compound of titanium is preferred. Further, when the titanium complex is dissolved in water, it is a compound which is coordinated to form a complex compound on titanium. Further, after the heat treatment, in order to retain the above-mentioned carbon compound on the surface of the composite oxide particle containing surface-modified lithium, the titanium compound is preferably a carbon-containing titanium complex compound to have a carbonyl group or a carbonic acid-15. - 200818581 The carbon-containing titanium coordination compound is more preferred, and the organic acid titanium coordination compound having a carbonyl group or a carbonic acid group is preferred. Specifically, the titanium compound is preferably at least one selected from the group consisting of titanium citrate, titanium tartrate, titanium oxalate, titanium malonate, titanium maleate, titanium malate, titanium gluconate, titanium lactate and titanium phthalate. Among them, the titanium compound is more preferably titanium lactate. The presence of the carbon preferably has a tendency to further improve the charge-discharge cycle characteristics of the composite oxide containing surface-modified lithium. Further, the Ti aqueous solution may contain a carboxylic acid. When the carboxylic acid is contained in the Ti aqueous solution, the carboxylic acid is preferably a carboxylic acid having a carbon number of 2 to 8 in terms of solubility in an aqueous solution, and at least one selected from the group consisting of citric acid, tartaric acid, oxalic acid, and acrylic acid. , maleic acid, malic acid, grape acid, lactic acid and titanium glyoxylate are better. The content of the carboxylic acid in the Ti aqueous solution is preferably 〜·〇 5 to 30% by weight, more preferably 〇·1 to 20% by weight. When the carboxylic acid is contained in the Ti aqueous solution, the solubility of the titanium complex contained in the Ti aqueous solution in water is improved, and the titanium complex which is not easily dissolved in the Ti aqueous solution tends to be precipitated.
Ti水溶液中鈦之濃度,就必須在繼後之步驟中藉由 乾燥除去水介質而言,以高濃度者較佳。然而,水溶液中 鈦之濃度過局時’黏度變_,與上述之母材進行接觸處理 或水溶液之處理性會有變得複雜的傾向。因此,Ti水溶 液中欽之濃度以0.01〜20重量%較佳,其中以〇·ΐ〜5重 量%更佳。 對母材之含鋰複合氧化物粒子而言,於含浸Ti水溶 液之步驟中,T i水溶液之量對使用的母材而言,以調製 -16- 200818581 於0.1〜80重量%之範圍較佳,以調製於1〜75重量%更 佳,其中以調製於30〜70重量%最佳。對使用的母材而 言Ti水溶液之量在上述範圍內時’大量合成本發明之正 極活性物質時,由於在批量間可解決正極活性物質之性能 不均勻性的問題,且可安定地量產正極活性物質的傾向, 故較佳。 對母材之含鋰複合氧化物粒子而言,含浸Ti水溶液 之方法,沒有特別的限制,具體而言可使用使Ti水溶液 以噴霧器噴霧於母材之粒子粉末中予以含浸的方法,或於 收容在容器中之Ti水溶液中投入母材之粒子粉末,且進 行攪拌予以含浸的方法等。攪拌時所使用的具體攪拌機, 例如2軸旋轉混練機、軸向混合機、攪拌混合機、渦流混 合機、桶混合機、固定空氣機、分級混合機等。 在母材之含鋰複合氧化物粒子中含浸Ti水溶液,再 進行混合·乾燥的步驟中,乾燥以在50〜200°C下進行較 佳,以80〜l4〇°C之溫度下更佳,且以0·1〜10小時之範 圍進行更佳。爲使乾燥後之鈦配位化合物含浸粒子中殘存 的水介質,在繼後的燒成步驟中予以除去時,在該階段中 不一定必須完全除去,惟爲在熱處理步驟中使水分予以氣 化時必須使用多量的能量,以儘可能除去者較佳。 而且,使Ti水溶液含浸,再進行混合•乾燥以製得 鈦配位化合物含浸粒子的步驟中,可以個別順序進行含浸 •混合•乾燥,亦可以全部同時使用分級混合機等予以進 行。 -17- 200818581 另外,儘可能自上述鈦配位化合物含浸粒子除去水媒 體後,在含氧之氣體環境中藉由較佳者2 00〜45 0°C、通常 〇· 1〜24小時下使鈦配位化合物含浸粒子進行熱處理,可 得本發明含表面修飾鋰之複合氧化物。而且,使上述含浸 粉末進行熱處理時,以溫度範圍爲250〜4001之範圍更佳 〇 由如上述所得的本發明含表面修飾鋰之複合氧化物粒 子所成的正極活性物質,其平均粒徑(D50)以5〜25μιη 較佳,以8〜20μιη更佳,比表面積以0· 1〜1.0m2/g較佳 ,以0.2〜0.8m2/g更佳。此外,藉由以CuKot作爲線源之 X線繞射所測定的2Θ = 65.1±1°之(110)面的繞射波峰半 値寬度爲 〇.〇8〜0.30°較佳,以0.09〜0.25°更佳。壓製密 度以2·40〜3.50g/cm3較佳,以2.50〜3.30g/cm3更佳。於 本發明中,壓製密度係指使表面修飾鋰複合氧化物粒子以 0.3 3噸/cm2之壓力進行壓製時粒子之表觀密度。而且, 本發明之含表面修飾鋰之複合氧化物的鋰離子溶出量,以 0·6〇莫耳%以下較佳,以〇.〇1〜0.50莫耳%更佳,其中以 0.01〜0·40莫耳%最佳。 於本發明中,鋰離子溶出量可如下述予以測定。首先 ,使l〇g正極活性物質之粉末加入90g水中,使所得的水 溶液進行攪拌30分鐘予以分散。然後,使該水溶液過濾 ,使所得的過濾液以鹽酸滴定求取。 鋰離子溶出量在上述範圍內時,正極活性物質粉末於 正極加工處理時,使正極活性物質粉末分散於N-甲基吡 -18- 200818581 咯烷酮等之分散媒的漿料,由於會有不易形成凝膠狀的傾 向,使正極加工處理變得更爲容易,故較佳。而且,以可 提高充放電循環特性之傾向較佳。 於本發明中’平均粒徑係指以體積基準求取粒度分布 ’以全部體積爲.100%之累積曲線中,該累積曲線爲50% 時點的粒徑,體積基準累積5 0%直徑(D50)。粒度分布 係指以雷射散射粒度分布測定裝置所測定的頻率分布及累 積體積分布曲線求取。粒徑之測定係藉由使粉末在水介質 中以超音波處理等充分進行分散,測定粒-度分布(例如使 用日機裝公司製微追跡HR A ( X- 1 00 )等)予以進行。而 且,於本說明書中,上述平均粒徑稱爲平均粒徑(D50) 或D5 0。另外,D10係表示上述累積曲線爲10%時點之粒 徑,D90係表示上述累積曲線爲90%時點之粒徑。 使用本發明之正極活性物質,製得鋰蓄電池用之正極 的方法,可以常法實施。例如,藉由在本發明正極活性物 質之粉末中,混合乙炔黑、黑鉛、廚房黑等之碳系導電材 料、與結合材料混合,形成正極合劑。在上述結合材料中 ,以使用聚氟化次乙烯基、聚四氟化乙烯、聚醯胺、羧基 甲基纖維素、丙烯酸樹脂等較佳。 使上述之正極合劑分散於N-甲基吡咯烷酮等之分散 媒的漿料,在鋁箔等之正極集電體上進行塗覆•乾燥及壓 製壓延,在正極集電體上形成正極活性物質層。 使用本發明之正極活性物質作爲正極的鋰蓄電池中, 電池之電解質溶液或聚合物電解質中所含的電解質,以使 -19- 200818581 用 1 種以上選自 C104_、CF3SO3-、BF4·、PF6-、AsF6·、 SbF6_、CF3C02_’(CF3S02)2N_等作爲陰離子之鋰鹽較佳。 電池之電解質溶液或聚合物電解質,以在溶劑或含有溶劑 之聚合物中含有0.2〜2.0mol/L之濃度由上述鋰鹽所成的 電解質較佳。脫離該範圍時,離子傳導度降低、且電解質 之電氣傳導度降低。更佳者爲選自0.5〜1.5mol/L。分離 器以多孔質聚乙烯、多孔質聚丙烯薄膜較佳。 此外,電解質溶液之溶劑,以碳酸酯較佳。碳酸酯可 使用環狀、或鏈狀。環狀碳酸酯例如碳酸丙二酯、碳酸乙 二酯(EC )等。鏈狀碳酸酯例如二甲基碳酸酯、二乙基 碳-酸酯(DEC )、乙基甲基碳酸酯、甲基丙基碳酸酯、甲 基異丙基碳酸酯等。 上述碳酸酯可以單獨使用,或2種以上混合使用。另 外,亦可與其他溶劑混合使用。而且,視負極活性物質之 材料而定,倂用鏈狀碳酸酯與環狀碳酸酯時,可改良放電 特性、充放電循環特性、充放電效率。 另外,亦可藉由在此等之有機溶劑中添加氟化次乙 烯-六氟化丙烯共聚物(例如亞頓肯姆(譯音)公司製凱 納(譯音))、氟化次乙烯-全氟丙基乙烯醚共聚物,且 加入下述之溶質,作爲凝膠聚合物電解質。 使用本發明之正極活性物質作爲正極的鋰電池之負極 活性物質,係爲可吸藏、放出鋰離子之材料。形成負極活 性物質之材料,沒有特別的限制,例如以鋰金屬、鋰合金 、碳材料、碳化合物、碳矽化合物、氧化矽化合物、硫化 -20 - 200818581 鈦、碳化硼化合物、週期表第14、15族之金屬作爲主體 之氧化物等。 碳材料可使用在各種熱分解條件下使有機物進行熱分 解者或人造黑鉛、天然黑鉛、土壤黑鉛、膨脹黑鉛、鱗片 狀黑鉛等。而且,氧化物可使用以氧化錫爲主體之化合物 。負極集電體係使用銅箔、鎳箔等。 使用本發明之正極活性物質的鋰蓄電池之形狀,沒有 特別的限制。可視用途而定,選擇片板狀(即薄膜狀)、 摺I狀、捲回型有底圓筒形,釦子形等。 【實施方式】 於下述中具體地說明本發明,惟本發明不受此等實施 例所限制、所解釋者。例1〜例3、例6、例8、例10、 例12、例14及例1 6係爲本發明之實施例,例4、例5、 例7、例9、例1 1、例13、例1 5及例17係爲比較例。 〔實施例〕 〔例1〕 使含有硫酸鎳與硫酸鈷與硫酸錳之硫酸鹽水溶液、及 硫酸銨水溶液、與氫氧化鈉水溶液,使反應槽內之漿料的 pH値爲11 ·0、溫度爲50°C下進行攪拌且各連續供應給反 應槽。以過量流動反應調整反應系內之液量,藉由使過量 流動的共沉澱漿料進行過濾、水洗,然後,在8 〇 t:下進行 乾燥,製得鎳鈷錳複合氫氧化物粉末。 -21 - 200818581 其次,藉由使該複合氫氧化物粉末分散於含有3重量 %氫氧化鈉之6重量%過硫酸鈉水溶液中,在20°C下進行 攪拌1 2小時,合成鎳鈷錳複合羰基氫氧化物漿料。再藉 由使該複合羰基氫氧化物漿料進行過濾、水洗,然後,進 ^ 行乾燥,製得複合羰基氫氧化物粉末,該複合羰基氫氧化 ' 物粉末之比表面積爲9.6 m2 / g、平均粒徑爲1〇.101!1。 在該所得的複合羰基氫氧化物粉末中以所定量混合平 φ 均粒徑20μπι之碳酸鋰粉末,在氧濃度爲40體積%之氣氛 環境中、1 000 °C下燒成16小時後,藉由粉碎,製得由含 有具LimXNimComMnwOmO;^之組成的含鋰複合氧化 物所成之母材。有關該母材,測定使用CuKa線之粉末X 線繞射光譜時,可知爲類似菱面體系(R-3m )之構造。 此外,測定係使用理學電機公司製RINT 2100型。有關該 母材粉末之粒子,進行SEM觀察時,可知多數一次粒子 凝聚形成二次粒子,且其形狀大約爲球狀或橢圓狀。 • 然後,在〇.61g鈦含量爲8.2重量%之乳酸鈦水溶液 中加入49.3 9g水,調製pH値2.1之Ti水溶液。藉由使 l〇〇g上述母材浸漬於50g上述Ti水溶液後,慢慢地混合 ,製得混合粉末。此外,使該混合粉末在120°C下乾燥4 * 小時,製得鈦配位化合物含浸粒子。使該經乾燥的配位化 合物含浸粒子在含氧之氣體環境中、3 5 0°C下進行加熱12 小時,平均粒徑爲 1〇.3μηι、D10 爲 5.2μιη、D90 爲 14.3μιη、比表面積爲0.5m2/g之約爲球狀的本發明含表面 修飾鋰之複合氧化物粒子。 -22- 200818581 有關所得的含表面修飾鋰之複合氧化物粒子’使用χ 線繞射裝置(理學電機公司製RINT 2100型),製得X 線繞射光譜。使用 CuKa線之粉末 X線繞射中, 2Θ = 65·1±1°之(110)面的繞射波峰半値寬度爲〇·225°。該 粒子之壓製密度爲2.7g/cm3。而且,該含表面修飾鋰之化 物粒子全體中所含的鈦,對鎳、锰及鈷合計量而言,以原 子比例爲0.0 0 1。 有關所得的含表面修飾鋰之複合氧化物粒子,藉由 XP S分析法測定該含鋰之複合氧化物粒子的表面之原子比 例(Ti/N )時,(Ti/N ) =0.7 1。此外,鋰離子溶出量爲 0.2 1莫耳%。 上述含表面修飾鋰之複合氧化物粒子、與乙炔黒、聚 氟化次乙烯粉末以90/5/5之重量比混合,且添加N-甲基 吡咯烷酮,製作漿料,在厚度爲20μχη之鋁箔上使用刮刀 進行單面塗覆。藉由進行乾燥、輥壓製壓延3次,製作鋰 電池用正極體薄片。 然後,用上述正極體薄片經穿孔者作爲正極,使用厚 度5 00μιη之金屬鋰箔作爲負極,使用20μιη鎳箔作爲負極 集電體,使用厚度2 5 μπι之多孔質聚丙烯作爲分離器,以 及使用濃度1Μ之LiPF6/EC + DEC ( 1:1 )溶液(係指以 1^1^6爲溶質之EC與DEC的重量比(1:1)之混合溶液。 下述之溶劑亦以此等爲基準。)作爲電解液,在氬氣小型 工具箱內組裝4個不鏽鋼製簡易密閉晶胞型鋰電池。 有關上述1個電池,在25 °C下使1 g正極活性物質以 -23- 200818581 3 0m A負荷電流充電至4 · 3 V,使1 g正極活性物質以3〇111八 負荷電流放電至2.5 V ’求取初期放電容量。此外,有關 該電池,進行30次充放電循環試驗。結果,在25艺、2· 5 〜4.3 V之正極活性物質的初期重量容量密度爲1 5 9m Ah/g ,30次充放電循環後之容量維持率爲98.5%。另外,有關 一個電池,除使充電電壓自4.3V改爲4.5V、進行25次 充放電循環試驗外,進行相同操作的結果,2.5〜4.5 V之 正極活性物質的初期重量容量密度爲175m Ah/g,進行25 次充放電循環後之容量維持率爲94.9%。 此外,有關另一電池係各以4.3 V及4.5 V進行充電 1 0小時,在氬氣小型工具箱內解體,取出充電後之正極 體薄片,且使該正極體薄片洗滌後,穿孔成直徑3mm, 在EC與鋁製膠囊內予以密閉,且以掃描型差動熱量計、 以5°C/分之速度予以昇溫,測定發熱開始溫度。結果, 4.3V充電品之發熱曲線的發熱開始溫度爲233 °C,4.5 V充 電者爲198°C。 〔例2〕 與例1相同地’合成母材之具有Lii.02(Nii/3C〇i/3Mni/3)0.98〇2 之組成的含鋰複合氧化物。 然後,在3.03g鈦含量爲8.2重量%之乳酸鈦水溶液 中加入4 6.9 7 g水,調製p Η値2之T i水溶液。藉由使 100g上述母材浸漬於50g上述Ti水溶液後,慢慢地混合 ,製得混合粉末。此外,使該混合粉末在120°C下乾燥4 -24- 200818581 小時,製得鈦配位化合物含浸粒子。使該經乾燥的配位化 合物含浸粒子在含氧之氣體環境中、350°C下進行加熱12 小時,平均粒徑爲 1 〇 · 5 μιη、D 1 0爲 5 · 5 μπι、D9 0爲 14·6μπι、比表面積爲〇.5m2/g之約爲球狀的本發明含表面 修飾鋰之複合氧化物粒子。 - 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKa線之粉末X線繞射 • 中,2Θ = 65·1 土 1。之(110)面的繞射波峰半値寬度爲0.226。 。該粒子之壓製密度爲2.69g/cm3。而-且,該含表面修飾 鋰之化物粒子全體中所含的鈦,對鎳、錳及鈷合計而言, 以原子比例爲0.0 0 5。 此外,有關所得的含表面修飾鋰之複合氧化物粒子, 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =1.50。此 外,鋰離子溶出量爲0.29莫耳%。 # 如上所述,於第1圖之IR光譜圖中,由於在1 3 00〜 1 700CHT1之範圍具有強的吸收波峰,故可知該含表面修飾 鋰之複合氧化物的表面層上有具碳-氧雙鍵之碳化合物存 在。 此外,藉由第2圖可知,乳酸鈦在3 00〜45 0°C下進行 分解反應,在500 °C下幾乎完成分解反應。 另外,由此等可知,於例2中藉由在3 50°C下進行熱 處理予以合成的含表面修飾鋰之複合氧化物粒子的表面層 上,有碳化合物存在。而且,可知爲使用以碳化合物作爲 -25 - 200818581 原料之含碳的鈦配位化合物之部分熱分解物。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在25 °C、2· 5〜4.3 V之正極活性物質的初期重 量容量密度爲159mAh/g,30次充放電循環後之容量維持 率爲9 8.3 %。 另外,在25°C、2.5〜4.5V之正極活性物質的初期重 量容量密度爲175mAh/g,進行25次充放電循環後之容量 維持率爲9 5.1 %。 此外,以掃描型差動熱量計、以5 °C /分之速度進行昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲23 5 °C,4.5V充電品之發熱開始溫度爲 2 00 〇C。 〔例3〕 Φ 與例1相同地,合成母材之具有 之組成的含鋰複合氧化物。 然後,在6 · 0 5 g鈦含量爲8.2重量%之乳酸欽水溶液 中加入43.95 g水,調製pH値2之Ti水溶液。藉由使 l〇〇g上述母材浸漬於50g上述Ti水溶液後,慢慢地混合 ,製得混合粉末。此外,使該混合粉末在120°C下乾燥4 小時,製得鈦配位化合物含浸粒子。使該經乾燥的配位化 合物含浸粒子在含氧之氣體環境中、3 5 0 °C下進行加熱1 2 小時,平均粒徑爲 10.7μιη、D10 爲 6.1μπι、D90 爲 -26- 200818581 15·〇μιη、比表面積爲0.5 5 m2/g之約爲球狀的本發明含表 面修飾鋰之複合氧化物粒子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKa線之粉末X線繞射 中,2Θ = 65·1±Γ之(110)面的繞射波峰半値寬度爲0.230。 。該粒子之壓製密度爲2.69g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鈦,對鎳、錳及鈷合計量而言 ,以原子比例爲0.01。 此τ外,有關所得的含表面修飾鋰之複合氧化物粒子, 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =3.30。此 外,鋰離子溶出量爲0.38莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在25°C、2·5〜4.3V之正極活性物質的初期重 量容量密度爲157mAh/g,30次充放電循環後之容量維持 率爲9 8 · 2 %。 另外,在25°C、2.5〜4.5V之正極活性物質的初期重 量容量密度爲173mAh/g,進行25次充放電循環後之容量 維持率爲95.1%。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫’測疋發熱開始溫度的結果,4.3 V充電品之發熱曲線 的發熱開始溫度爲234°C,4.5V充電品之發熱開始溫度爲 2 01〇C。 -27- 200818581 〔例4〕 與例1相同地,合成母材之具有LiuHNimComMm/Do.MC^ 之組成的含鋰複合氧化物。該母材之平均粒徑爲1 〇 . 5 μιη 、D10 爲 5.3μιη、D90 爲 1 3.5 μιη、比表面積爲 0.4 9m2/g 之一次粒子多數凝聚且形成二次粒子之粒子所成的粉末。 有關該複合氧化物粒子,使用X線繞射裝置(理學電機 公司製RINT 2100型),製得X線繞射光譜。使用CuKa 線之粉末X線繞射中,2Θ = 65·1土1°之(110 )面的繞射波 峰半値寬度爲0.225°。該粒子之壓製密度爲2.70g/cm3。 而且,對上述母材之含鋰的複合氧化物粒子而言,與 例1相同地藉由XPS分析法進行表面元素分析時,無法 檢測出鈦。 此外,如上所述於第1圖之IR光譜圖中,由於在 1 3 00〜1 700CHT1之範圍具有強的吸收波峰,故可知該鋰之 複合氧化物爲不含具有碳-氧雙鍵之碳化合物。 使用母材之含鋰的複合氧化物粒子,與例1相同地作 成正極薄片,且組裝電池進行評估。 結果,在2 5 °C、2 · 5〜4 · 3 V之正極活性物質的初期重 量容量密度爲160mAh/g,30次充放電循環後之容量維持 率爲9 5.0 %。 另外,在2 5 °C、2 · 5〜4 · 5 V之正極活性物質的初期重 量容量密度爲1 75mAh/g,·進行25次充放電循環後之容量 維持率爲9 1.0 %。 -28- 200818581 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲232°C,4.5V充電品之發熱開始溫度爲 199〇C 〇 〔例5〕 與例1相同地》合成母材之具有Lii.G2(Nii/3C〇i/3Mni/3)G.98〇2 之組成的含鋰複合氧化物。 然後,在〇.〇6g鈦含量爲8.2重量%之乳酸鈦水溶液 中加入49.94g水,調製!)11値2.5之14水溶液。藉由使 l〇〇g上述母材浸漬於50g上述Ti水溶液後,慢慢地混合 ,製得混合粉末。此外,使該混合粉末在1 20 °C下乾燥4 小時,製得鈦配位化合物含浸粒子。使該經乾燥的配位化 合物含浸粒子在含氧之氣體環境中、3 50°C下進行加熱12 小時,平均粒徑爲 10.4μιη、D10 爲 5.0μηι、D90爲 14.1μιη、比表面積爲0.48m2/g之約爲球狀的本發明含表 面修飾鋰之複合氧化物粒子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKa線之粉末X線繞射 中,2Θ = 65.1士 1。之(110)面的繞射波峰半値寬度爲0.224。 。該粒子之壓製密度爲2.70g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鈦,對鎳、錳及鈷合計量而言 ,以原子比例爲0.0 0 0 1。 此外,有關所得的含表面修飾鋰之複合氧化物粒子, -29- 200818581 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =0.18。此 外,鋰離子溶出量爲0.20莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 ‘ 結果,在25°c、2.5〜4.3V之正極活性物質的初期重 量容量密度爲160mAh/g,30次充放電循環後之容量維持 φ 率爲 9 5.2 %。 另外,在25°C、2.5〜4.5V之正極活性物質的初期重 量容量密度爲173 mAh/g,進行25次充放電循環後之容量 維持率爲91.2%。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3 V充電品之發熱曲線 的發熱開始溫度爲234°C,4.5V充電品之發熱開始溫度爲 201 °C ° 〔例6〕 使197.18g平均粒徑爲12.;^111、鈷含量爲61.0重量 %之氫氧化鈷、〇 · 1 6 g氫氧化鋁、〇 · 1 2 g氫氧化鎂、與 ' 75·91§比表面積爲I2m2/g之碳酸鋰粉末混合,在含氧之 氣體環境中、990 °C下燒成14小時後,藉由解碎,製得由 含有具LUCoojwAluHMg。㈣1)〇2之組成的含鋰複合氧化 物所成之母材。 然後’在〇.〇6g鈦含量爲8.2重量%之乳酸鈦水溶液 -30- 200818581 中加入50g水,調製pH値2·5之Ti水溶液。藉由使 1 〇〇g上述母材浸漬於上述Ti水溶液後,慢慢地混合,製 得混合粉末。此外,使該混合粉末在120 °c下乾燥4小時 ’製得鈦配位化合物含浸粒子。使該經乾燥的配位化合物 含浸粒子在含氧之氣體環境中、3 50°C下進行加熱12小時 ,平均粒徑爲 12·0μιη、D10 爲 6.7μπι、D90 爲 18·8μχη、 比表面積爲0.25m2/g之約爲球狀的本發明含表面修飾鋰 之複合氧化物粒子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKa線之粉末X線繞射 中,2Θ = 66.5±1。之(110)面的繞射波峰半値寬度爲0.108。 。該粒子之壓製密度爲3.0 2 g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鈦,對鎳、錳及鈷合計量而言 ,以原子比例爲0.0 0 1。 此外,有關所得的含表面修飾鋰之複合氧化物粒子, 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =1.26。此 外,鋰離子溶出量爲0.09莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在25°C、2.5〜4.3 V之正極活性物質的初期重 量容量密度爲157mAh/g,30次充放電循環後之容量維持 率爲99.8%。 另外,在25°C、2.5〜4.5V之正極活性物質的初期重 200818581 量容量密度爲184mAh/g,進行25次充放電循環後之容量 維持率爲97.0%。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲158°C,4.5V充電品之發熱開始溫度爲 146〇C ° 〔例7〕 使1 96.99g平均粒徑爲12.Ιμηι、鈷含量爲61.0重量 %之氫氧化鈷、0.1 6g氫氧化鋁、0.12g氫氧化鎂、與 〇.16g氧化鈦、75.91g比表面積爲1.2m2/g之碳酸鋰粉末 混合,在含氧之氣體環境中、990 °C下燒成•解碎14小時 後,製得由含有具 Li(C〇〇.997Al〇.〇〇iMg().〇()iTi〇.〇〇i)〇2 之組 成的含鋰複合氧化物。 該含鋰複合氧化物,係平均粒徑爲1〇.3μιη、D10爲 6.4μιη、D90爲1 5 ·4μπι、比表面積爲0.26m2/g之約爲球狀 〇 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKot線之粉末.X線繞射 中,2Θ = 66· 5士 Γ之(110)面的繞射波峰半値寬度爲0.097。 。該粒子之壓製密度爲3.0 9 g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鈦,對鈷、鋁、鎂及鈦合計量 而言,以原子比例爲0.001。 此外,有關所得的含表面修飾鋰之複合氧化物粒子, -32- 200818581 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =0.15。此 外,鋰離子溶出量爲0.1 0莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 * 結果,在2 5 °C、2 · 5〜4.3 V之正極活性物質的初期重 量容量密度爲159mAh/g,30次充放電循環後之容量維持 φ 率爲 9 6 · 9 %。 另外,在2 5 °C、2.5〜4.5 V之正極活性物質的初期重 量容量密度爲185mAli/g,進行25次充放電循環後之容量 維持率爲8 3.0 %。 此外,以掃描型差動熱量計、以5°C /分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲1S5°C,4.5V充電品之發熱開始溫度爲 145〇C。 〔例8〕 在51.03g水中使1.20g氫氧化鎂分散,進行攪拌且 各少量加入5 · 4 6 g檸檬酸予以溶解。然後,加入1 2.3 1 g 含量4 · 5重量%鋁之乳酸鋁水溶液予以混合,製得含有鋁 與鎂之水溶液(Al-Mg溶液)。 使1 96.62g平均粒徑爲12·0μχη、對銘含量爲60.3重 量%之鑛基氫氧化銘而言加入上述A1 - M g容易進行浸漬混 合,在120°C下進行乾燥4小時,製得含有鋁與鎂之羰基 -33- 200818581 氫氧化鈷粉末。 藉由使77.72g比表面積爲1.2m2/g之碳酸鋰粉末與含 有上述鋁與鎂之羰基氫氧化鈷粉末混合,在含氧之氣體環 境中、990°C下燒成14小時後,予以解碎,製得由含有具 Lil.G2(C〇G.98Al〇.〇lMg〇 ()l)G.98〇2之組成的塊狀含鍵複合氧 化物作爲母材。 然後,在〇.〇6g氫氧化鎂中加入50g水,進行攪拌且 各少量加入〇.14g檸檬酸予以溶解。然後,加入0.06g鈦 含-量爲8.2重量%之乳酸鈦水溶液,調製pH値2.5之含鎂 與鈦之水溶液(Mg-Ti水溶液)。藉由使100g上述母材 浸漬於上述Mg-Ti水溶液後,慢慢地混合,製得混合粉末 。此外,使該混合粉末在120 °C下乾燥4小時,製得鎂-鈦 配位化合物含浸粒子。使該經乾燥的配位化合物含浸粒子 在含氧之氣體環境中、4 0 0 °C下進行加熱12小時,平均粒 徑爲 12·6μιη、D10 爲 6.8μιη、D90 爲 19·0μιη、比表面積 爲0.3 0m2/g之約爲球狀的含表面修飾鋰之複合氧化物粒 子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKa線之粉末X線繞射 中,2Θ = 6 6.5土 Γ之(110)面的繞射波峰半値寬度爲0.108。 。該粒子之壓製密度爲3.03 g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鎂與鈦,對鈷、鋁及鎂合計量 而言,以原子比例爲0.002。此外,該含表面修飾鋰之複 合氧化物粒子全體中所含的鈦,對鈷、鋁及鎂之合計量而 -34- 200818581 W,以原子比例爲0.0 0 1。 此外,有關所得的含表面修飾鋰之複合氧化物粒子, 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) = 1 · 1 7。此 外,鋰離子溶出量爲0.20莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在25°c、2.5〜4.3V之正極活性物質的初期重 量容量密度爲151mAh/g,30次充放電循環後之容量維持 率爲9 9.5 %。 另外,在25 °C、2.5〜4.5V之正極活性物質的初期重 量容量密度爲178mAh/g,進行25次充放電循環後之容量 維持率爲9 5.2 %。 此外,以掃描型差動熱量計、以5 °C /分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲159°C,4.5V充電品之發熱開始溫度爲 147〇C。 〔例9〕 在5 0g水中使0.06g氫氧化鎂分散,進行攪拌且各少 量加入0.14g檸檬酸予以溶解,調製pH値爲4.0之Mg水 溶液。 藉由使 l〇〇g 以例 8 所合成的 Lii.G2(C〇Q.98AlG,()iMg〇.()i)().98〇2 之組成的含鋰複合氧化物浸漬於上述之Mg水溶液後,慢 -35- 200818581 慢地混合,製得混合粉末。此外,使該混合粉末在120°C 下乾燥4小時,製得鎂配位化合物含浸粒子。使該經乾燥 的配位化合物含浸粒子在含氧之氣體環境中、400 °C下進 行加熱12小時,平均粒徑爲11·8μιη、D10爲6.6μιη、D90 ' 爲17·8μπι、比表面積爲〇.23m2/g之約爲球狀的含表面修 . 飾鋰之複合氧化物粒子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 φ 相同地測定X線繞射光譜。使用CuKa線之粉末X線繞射 中,20 = 66.5士1。之(110)面的繞射波峰半値寬度爲0.10-4。 。該粒子之壓製密度爲3.06g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鎂,對鈷而言,以原子比例爲 0.001 〇 此外,有關所得的含表面修飾鋰之複合氧化物粒子, 與例1相同地藉由XPS分析法測定表面元素分析時,沒 有檢測出鈦。而且,鋰離子溶出量爲0.24莫耳%。 • 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在25°c、2.5〜4.3V之正極活性物質的初期重 量容量密度爲15 ImAh/g,30次充放電循環後之容量維持 ^ 率爲 9 9.0 %。 另外,在25°C、2.5〜4.5V之正極活性物質的初期重 量容量密度爲1 80 m Ah/g,進行25次充放電循環後之容量 維持率爲9 2.5 %。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 -36- 200818581 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲154°C,4.5V充電品之發熱開始溫度爲 144〇C ° 〔例 10〕 藉由在例1所得的複合羰基氫氧化物粉末中,使碳酸 鋰粉末以所定量混合,與例1相同地進行燒成、粉碎,合 成母材之具有之組成的含鋰 複合氧化物。 然後,在〇.61g鈦含量爲8.2重量%之乳酸鈦水溶液 中加入49.3 9g水,調製pH値2.1之Ti水溶液。藉由使 100g上述母材浸漬於50g上述Ti水溶液後,慢慢地混合 ,製得混合粉末。此外,使該混合粉末在120°C下乾燥4 小時,製得鈦配位化合物含浸粒子。使該經乾燥的配位化 合物含浸粒子在含氧之氣體環境中、3 50°C下進行加熱12 小時,平均粒徑爲 ΙΙ.Ομηι、D10爲 6.3μηι、D90爲 15·5μιη、比表面積爲0.49m2/g之約爲球狀的本發明含表 面修飾鋰之複合氧化物粒子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKa線之粉末X線繞射 中,20 = 65.1土1。之(110)面的繞射波峰半値寬度爲0.199。 。該粒子之壓製密度爲2.67g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鈦,對鎳、錳及鈷合計量而言 ,以原子比例爲〇 · 〇 〇 1。 -37- 200818581 此外,有關所得的含表面修飾鋰之複合氧化物粒子, 與例1相同地藉由xps分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =〇·7。此外 ,鋰離子溶出量爲0.38莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在2 5 °C、2.5〜4.3 V之正極活性物質的初期重 量容量密度爲157mAh/g,30次充放電循環後之容量維持 率爲9 8.5 %。 另外,在25°C、2.5〜4.5V之正極活性物質的初期重 量容量密度爲173 mAh/g,進行25次充放電循環後之容量 維持率爲94.5%。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲231 °C,4.5V充電品之發熱開始溫度爲 2 0 0 °C 〇 〔例 11〕 與例10相同地,合成母材之具有 之組成的含鋰複合氧化物。該母材之平均粒徑爲10.8 μπι 、D10 爲 6·1μπι、D90 爲 1 5 . 1 μηι、比表面積爲 0.47m2/g 之一次粒子多數凝聚且形成二次粒子之粒子所成的粉末。 有關該複合氧化物粒子,使用X線繞射裝置(理學電機 公司製RINT 2100型),製得X線繞射光譜。使用CuKa -38- 200818581 線之粉末X線繞射中,2Θ = 65·1土 Γ之(110)面的繞射波 峰半値寬度爲0.197°。該粒子之壓製密度爲2.70g/cm3。 而且,對上述母材之含鋰的複合氧化物粒子而言,與 例1相同地藉由XPS分析法進行表面元素分析時,無法 檢測出鈦。 使用上述母材之含鋰複合氧化物粒子,與例1相同地1 作成正極體,且組裝電池,進行評估。 結果,在2 5 °C、2.5〜4 · 3 V之正極活性物質的初期重 量容量密度爲1 59nrAh/g,30次充放電循環後之容量維持 率爲94.9%。 另外,在25°C、2.5〜4.5V之正極活性物質的初期重 量容量密度爲174mAh/g,進行25次充放電循環後之容量 維持率爲90.0%。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲23 0°C,4·5 V充電品之發熱開始溫度爲 198〇C ° 〔例 1 2〕 使含有鎳、鈷及錳之各元素比例調合爲NkC(KMn = 0.50:0.20:0.30之硫酸鎳與硫酸鈷與硫酸錳的硫酸鹽混合 水溶液、與硫酸銨水溶液與氫氧化鈉水溶液’使反應槽內 漿料之PH値爲11.0、溫度爲50 °C下進行攪拌且各連續供 應給反應槽。以過量流動方式調整反應系內之液量,使過 -39 - 200818581 量流動的共沉澱漿料進行過濾、水洗,然後,在80°C下進 行乾燥,製得鎳鈷錳複合氫氧化物粉末。 其次,藉由使該複合氫氧化物粉末分散於含有3重量 %氫氧化鈉之6重量%過硫酸鈉水溶液,在20°C下進行攪 拌12小時,合成鎳鈷錳複合羰基氫氧化物漿料。另外, 使該複合羰基氫氧化物漿料進行過濾、水洗,然後,予以 乾燥,製得複合羰基氫氧化物粉末。該複合羰基氫氧化物 粉末之比表面積爲9.4m2/g,平均粒徑爲9.5μπι。 藉由在如此所得的複合羰基氫氧化物粉末中,以所定 量混合平均粒徑20μιη之碳酸鋰粉末,在含氧之氣體環境 中、970 °C下進行燒成12小時後,予以粉碎,製得由含有 具Lh.oKNio.sCoo.iMno.Oo.^C^之組成的含鋰複合氧化物 所成之母材。有關該母材,使用CuKa線測定粉末又線繞 射光譜時,可知爲表面體系(R-3m )之類似構造。而且 ,測定時係使用理學電機公司製RINT 2 100型。有關該母 材粉末之粒子,進行SEM觀察時,多數一次粒子凝聚形 成二次粒子者,且其形狀爲大約球形或橢圓形。 其次,然後,在〇.60g鈦含量爲8.2重量%之乳酸鈦 水溶液中加入49.40g水,調製pH値2.1之Ti水溶液。 藉由使l〇〇g上述母材浸漬於50g上述Ti水溶液後,慢慢 地混合,製得混合粉末。此外,使該混合粉末在120°C下 乾燥4小時,製得鈦配位化合物含浸粒子。使該經乾燥的 配位化合物含浸粒子在含氧之氣體環境中、3 50°C下進行 加熱12小時,平均粒徑爲9·2μπι、D10爲5·2μιη、D90爲 -40- 200818581 15·0μιη、比表面積爲0.52m2/g之約爲球狀的本發明含表 面修飾鋰之複合氧化物粒子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKoi線之粉末X線繞射 中,2Θ = 65.1±Γ之(110)面的繞射波峰半値寬度爲0.13 9。 。該粒子之壓製密度爲2.65g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鈦,對鎳、錳及鈷合計量而言 ,以原子比例爲0.001。 此外,有關所得的含表面修飾鋰之複合氧化物粒子, 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =0.69。此 外,鋰離子溶出量爲0.59莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在25°C、2.5〜4.3V之正極活性物質的初期重 量容量密度爲165mAh/g,30次充放電循環後之容量維持 率爲9 7 · 5 %。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲2〇2°C。 〔例 1 3〕 與例12相同地,合成母材之具有Lii.Gi(NiG.5C〇G.2Mn().3)().99〇2 之組成的含鋰複合氧化物。該母材之平均粒徑爲8.9Pm、 -41 - 200818581 D10 爲 5.0μιη、D90 爲 1 4 · 9 μιη、比表面積爲 Ο · 5 0m2/g 之 一次粒子多數凝聚且形成二次粒子之粒子所成的粉末。有 關該複合氧化物粒子,使用X線繞射裝置(理學電機公 司製RINT 2 100型),製得X線繞射光譜。使用CuKa線 之粉末X線繞射中,2Θ = 65.1±Γ之(110 )面的繞射波峰 半値寬度爲0.135°。該粒子之壓製密度爲2.69g/cm3。 而且,對上述母材之含鋰的複合氧化物粒子而言,與 例1相同地藉由XPS分析法進行表面元素分析時,無法 檢測出鈦。 使用上述母材之含鋰複合氧化物粒子,與例1相同地 作成正極體,且組裝電池,進行評估。 結果,在25°C、2·5〜4.3V之正極活性物質的初期重 量容量密度爲168mAh/g,30次充放電循環後之容量維持 率爲9 6.0 %。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫’測疋發熱開始溫度的結果,4.3 V充電品之發熱曲線 的發熱開始溫度爲201°C。 〔例 1 4〕 使含有鎳、鈷及錳之各元素比例調合爲Ni: Co: Mn = 03 5:0.40:0.25之硫酸鎳與硫酸鈷與硫酸錳的硫酸鹽混合水 溶液、與硫酸銨水溶液與氫氧化鈉水溶液,使反應槽內漿 料之pH値爲11.0、溫度爲50°C下進行攪拌且各連續供應 給反應槽。以過量流動方式調整反應系內之液量,使過量 -42- 200818581 流動的共沉澱漿料進行過濾、水洗,然後,在80°C下進行 乾燥,製得鎳鈷錳複合氫氧化物粉末。 其次,藉由使該複合氫氧化物粉末分散於含有3重量 %氫氧化鈉之6重量%過硫酸鈉水溶液,在20°C下進行攪 拌1 2小時,合成鎳鈷錳複合羰基氫氧化物漿料。另外, 使該複合羰基氫氧化物漿料進行過濾、水洗,然後,予以 乾燥,製得複合羰基氫氧化物粉末。該複合羰基氫氧化物 粉末之比表面積爲9.4m2/g,平均粒徑爲9.5μπι。 藉由在如此所得的複合羰基氫氧化物粉末中,以所定 量混合平均粒徑20μηι之碳酸鋰粉末,在含氧之氣體環境 中、990 °C下進行燒成12小時後,予以粉碎,製得由含有 具LiuKNimCOo.4(^11().25)().9902之組成的含鋰複合氧化 物所成之母材。有關該母材,使用CuKa線測定粉末X線 繞射光譜時,可知爲表面體系(R-3m )之類似構造。而 且,測定時係使用理學電機公司製RINT 2 1 00型。有關該 母材粉末之粒子,進行SEM觀察時,多數一次粒子凝聚 形成二次粒子者,且其形狀爲大約球狀或橢圓狀。 其次,然後,在〇.60g鈦含量爲8.2重量%之乳酸鈦 水溶液中加入49· 40g水,調製pH値2.1之Ti水溶液。 藉由使l〇〇g上述母材浸漬於5(^上述1^水溶液後,慢慢 地混合,製得混合粉末。此外,使該混合粉末在120°C下 乾燥4小時,製得鈦配位化合物含浸粒子。使該經乾燥的 配位化合物含浸粒子在含氧之氣體環境中、3 50°C下進行 加熱12小時,平均粒徑爲ΙΟ.Ιμηι、D10爲5.0μπι、D90 -43- 200818581 爲14·1μπι、比表面積爲0.46m2/g之約爲球狀的本發明含 表面修飾鋰之複合氧化物粒子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CiiKa線之粉末X線繞射 中,2Θ = 65·1±Γ之(110 )面的繞射波峰半値寬度爲0.22。 。該粒子之壓製密度爲2.72g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的鈦,對鎳、錳及鈷合計量而言 ,以原子比例爲0.0 0 1。 此外,有關所得的含表面修飾鋰之複合氧化物粒子, 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =0·72。此 外,鋰離子溶出量爲0.35莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在25°C、2.5〜4.3V之正極活性物質的初期重 量容量密度爲153mAh/g,30次充放電循環後之容量維持 率爲9 7 · 3 %。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲1 9 1°C。 〔例 1 5〕 與例14相同地,合成母材之具有Lii.oKNio.hCocMoMnuOGMCb 之組成的含鋰複合氧化物。該母材之平均粒徑爲9·9 μηι、 -44- 200818581 D10 爲 4·9μπι、D90 爲 13·9μπι、比表面積爲 0.40m2/g 之 一次粒子多數凝聚且形成二次粒子之粒子所成的粉末。有 關該複合氧化物粒子,使用X線繞射裝置(理學電機公 司製RINT 2100型),製得X線繞射光譜。使用CuKa線 之粉末X線繞射中,2Θ = 65·1±1。之(110 )面的繞射波峰 半値寬度爲0.219°。該粒子之壓製密度爲2.75g/cm3。 而且,對上述母材之含鋰的複合氧化物粒子而言’與 例1相同地藉由XPS分析法進行表面元素分析時’無法 檢測出鈦。 使用上述母材之含鋰複合氧化物粒子,與例1相同地 作成正極體,且組裝電池,進行評估。 結果,在25°C、2.5〜4.3V之正極活性物質的初期重 量容量密度爲155mAh/g,30次充放電循環後之容量維持 率爲9 6.0 %。 此外,以掃描型差動熱量計、以5t:/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲190°C。 〔例 1 6〕 使含有鎳、銘及鍤之各兀素比例調合爲N i: C 〇 : Μ η = 〇·3 0:0.30 :0.40之硫酸鎳與硫酸鈷與硫酸錳的硫酸鹽混合 水溶液、與硫酸銨水溶液與氫氧化鈉水溶液,使反應槽內 漿料之p Η値爲1 1.0、溫度爲5 〇 °C下進行攪拌且各連續供 應給反應槽。以過量流動方式調整反應系內之液量,使過 -45- 200818581 量流動的共沉澱漿料進行過濾、水洗,然後,在8〇 t:下進 行乾燥,製得鎳鈷錳複合氫氧化物粉末。 其次,藉由使該複合氫氧化物粉末分散於含有3重量 %氫氧化鈉之6重量%過硫酸鈉水溶液,在2 0 °C下進行攪 拌1 2小時,合成鎳鈷錳複合羰基氫氧化物漿料。另外, 使該複合羰基氫氧化物漿料進行過濾、水洗,然後,予以 乾燥,製得複合羰基氫氧化物粉末。該複合羰基氫氧化物 粉末之比表面積爲l〇.8m2/g,平均粒徑爲9.0μπι。 藉由在如此所得的複合羰基氫氧化物粉末中,以所定 量混合平均粒徑20μιη之碳酸鋰粉末,在含氧之氣體環境 中、95 0°C下進行燒成12小時後,予以粉碎,製得由含有 具之組成的含鋰複合氧化物 所成之母材。有關該母材,使用CxiKa線測定粉末X線繞 射光譜時,可知爲表面體系(R-3m )之類似構造。而且 ,測定時係使用理學電機公司製RINT 2100型。有關該母 材粉末之粒子,進行SEM觀察時,多數一次粒子凝聚形 成二次粒子者,且其形狀爲大約球狀或橢圓狀。 其次,然後,在〇.61g鈦含量爲8.2重量%之乳酸鈦 水溶液中加入49.3 9g水,調製pH値2· 1之Ti水溶液。 藉由使100g上述母材浸漬於50g上述Ti水溶液後,慢慢 地混合,製得混合粉末。此外,使該混合粉末在120 °C下 乾燥4小時,製得鈦配位化合物含浸粒子。使該經乾燥的 配位化合物含浸粒子在含氧之氣體環境中、3 5 0 °C下進行 加熱12小時,平均粒徑爲9·0μπι、D10爲4·5μπι、D90爲 -46- 200818581 14.8μπι、比表面積爲〇.65m2/g之約爲球狀的本發明含表 面修飾鋰之複合氧化物粒子。 有關所得的含表面修飾鋰之複合氧化物粒子,與例1 相同地測定X線繞射光譜。使用CuKa線之粉末X線繞射 中,20 = 65.1±1°之(11〇)面的繞射波峰半値寬度爲〇.272° 。該粒子之壓製密度爲2.5 1 g/cm3。而且,該含表面修飾 鋰之化物粒子全體中所含的欽,對鎳、锰及銘合計量而言 ,以原子比例爲0.00 1。 此外,有關所得的含表面修飾鋰之複合氧化物粒子t 與例1相同地藉由XPS分析法測定該含鋰之複合氧化物 粒子的表面之原子比例(Ti/N )時,(Ti/N ) =0.70。此 外,鋰離子溶出量爲0.3 7莫耳%。 正極體薄片係除使用上述含表面修飾鋰之複合氧化物 所製作者外,與例1相同地製作電極及電池且進行評估。 結果,在25°C、2.5〜4.3V之正極活性物質的初期重 量容量密度爲140mAh/g,30次充放電循環後之容量維持 率爲9 7.8 %。 此外,以掃描型差動熱量計、以5°C/分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲240 °C。 〔例 1 7〕 •與例 16 相同地,合成母材之具有 Lii.〇l(Ni〇.3GC〇G.3()Mn〇.4G)G.99〇2 之組成的含鋰複合氧化物。該母材之平均粒徑爲8 · 5 μιη、 -47- 200818581 D10 爲 4·5μιη、D90 爲 14·2μιη、比表面積爲 〇.62m2/g 之 一次粒子多數凝聚且形成二次粒子之粒子所成的粉末。有 關該複合氧化物粒子,使用X線繞射裝置(理學電機公 司製RINT 2100型),製得X線繞射光譜。使用CuKa線 之粉末X線繞射中,2Θ = 65·1士Γ之(110 )面的繞射波峰 半値寬度爲〇.27°。該粒子之壓製密度爲2.55g/cm3。 而且,對上述母材之含鋰的複合氧化物粒子而言,與 例1相同地藉由XPS分析法進行表面元素分析時,無法 檢測出鈦。 使用上述母材之含鋰複合氧化物粒子,與例1相同地 作成正極體,且組裝電池,進行評估。 結果,在25°C、2.5〜4.3V之正極活性物質的初期重 量容量密度爲142mAh/g,30次充放電循環後之容量維持 率爲9 6 · 1 %。 此外,以掃描型差動熱量計、以5 °C /分之速度予以昇 溫,測定發熱開始溫度的結果,4.3V充電品之發熱曲線 的發熱開始溫度爲23 9°C。 〔產業上之利用價値〕 藉由本發明,可提供一種不會降低高安全性、具有高 運作電壓、高放電容量及優異的充放電循環特性之由含鋰 複合氧化物粒子所成的非水電解質蓄電池用正極活性物質 ,該正極活性物質製造方法以及使用該正極活性物質之非 水電解質蓄電池。 -48- 200818581 而且,此處引用2006年7月26日所申請的日 申請20 06-2 03 99 3號及20 06年8月3日所申請的 利申請2006-212647號說明書、專利申請範圍、圖 明書之全部內容,且應用於本發明說明書之揭示中 【圖式簡單說明】 〔第1圖〕係表示以例2 (實施例)所得的含 飾鋰複合氧化物之紅外線吸收(IR )光譜(A )及 (比較例)所得的含鋰複合氧化物之紅外線吸收( 譜(B ) 〇 〔_第2圖〕係表示經乾燥的乳酸鈦之熱重量 示差重量(TG-DTA-DTG)分析的測定結果。 本專利 曰本專 面及說 表面修 以例4 IR)光 我差熱- -49 -The concentration of titanium in the Ti aqueous solution is preferably at a high concentration in the subsequent step by removing the aqueous medium by drying. However, when the concentration of titanium in the aqueous solution is too small, the viscosity is changed, and the contact with the above-mentioned base material or the rationality of the aqueous solution tends to be complicated. Therefore, the concentration of the solution in the Ti aqueous solution is 0. 01 to 20% by weight is more preferable, and more preferably 5% by weight. For the lithium-containing composite oxide particles of the base material, in the step of impregnating the aqueous solution of Ti, the amount of the aqueous solution of Ti is used for the base material used to modulate -16-200818581 to 0. The range of 1 to 80% by weight is preferably adjusted to be 1 to 75% by weight, more preferably 30 to 70% by weight. When the amount of the Ti aqueous solution used is within the above range, when the positive electrode active material of the present invention is synthesized in a large amount, the problem of the performance unevenness of the positive electrode active material can be solved between batches, and the mass production can be stably performed. The tendency of the positive electrode active material is preferred. The method of impregnating the Ti-containing aqueous solution of the lithium-containing composite oxide particles of the base material is not particularly limited, and specifically, a method in which the Ti aqueous solution is sprayed in the particle powder of the base material by a sprayer can be used, or can be contained. A method of impregnating a particle powder of a base material into a Ti aqueous solution in a container, stirring it, and so on. The specific agitator used for stirring, such as a 2-axis rotary kneading machine, an axial mixer, a stirring mixer, a vortex mixer, a barrel mixer, a fixed air machine, a stage mixer, and the like. In the step of mixing and drying the lithium-containing composite oxide particles of the base material, the step of mixing and drying is preferably carried out at 50 to 200 ° C, preferably at a temperature of 80 to 14 ° C. It is more preferably in the range of 0·1 to 10 hours. In order to impregnate the residual aqueous medium in the particles after drying, the titanium medium is removed in the subsequent firing step, and it is not necessary to completely remove it in this stage, but the water is vaporized in the heat treatment step. A large amount of energy must be used in order to remove as much as possible. Further, in the step of impregnating the Ti aqueous solution and further mixing and drying to obtain the titanium complex compound impregnated particles, the impregnation, mixing, and drying may be carried out in an individual order, or may be carried out by using a classification mixer at the same time. -17- 200818581 In addition, as far as possible, the water medium is removed from the titanium complex compound impregnated particles, and is preferably used in an oxygen-containing gas atmosphere by a temperature of 200 to 45 ° C, usually 〇 1 to 24 hours. The surface-modified lithium-containing composite oxide of the present invention can be obtained by heat-treating the titanium complex compound impregnated particles. Further, when the impregnated powder is subjected to heat treatment, the positive electrode active material of the surface-modified lithium-containing composite oxide particles of the present invention obtained as described above is preferably in a temperature range of from 250 to 4001, and the average particle diameter thereof is D50) is preferably 5~25μηη, more preferably 8~20μηη, and the specific surface area is 0·1~1. 0m2/g is better, with 0. 2~0. 8m2/g is better. In addition, 2 Θ = 65 is determined by X-ray diffraction with CuKot as the line source. The diffraction peak width of the (110) plane of 1±1° is 値. 〇8~0. 30° is better, with 0. 09~0. 25° is better. The compaction density is 2·40~3. 50g/cm3 is preferred, with 2. 50~3. 30g/cm3 is better. In the present invention, the compacted density means that the surface-modified lithium composite oxide particles are 0. The apparent density of the particles when pressed at a pressure of 3 tons/cm2. Further, the amount of lithium ion elution of the surface-modified lithium-containing composite oxide of the present invention is preferably 0.6% by mole or less. 〇1~0. 50% Mo is better, with 0. 01~0·40 mol% is the best. In the present invention, the amount of lithium ion eluted can be measured as described below. First, a powder of 10 g of the positive electrode active material was added to 90 g of water, and the resulting aqueous solution was stirred for 30 minutes to be dispersed. Then, the aqueous solution was filtered, and the obtained filtrate was titrated with hydrochloric acid. When the amount of lithium ion elution is in the above range, the positive electrode active material powder is dispersed in a slurry of a dispersion medium such as N-methylpyr-18-200818581-rrolidone during the positive electrode processing. It is preferable that the gelation tends not to be formed, and the positive electrode processing is made easier. Further, the tendency to improve the charge and discharge cycle characteristics is preferable. In the present invention, the 'average particle size means that the particle size distribution is determined on a volume basis'. In the 100% cumulative curve, the cumulative curve is the particle size at 50%, and the volume basis is accumulated at 50% diameter (D50). The particle size distribution is determined by the frequency distribution and the cumulative volume distribution curve measured by the laser scattering particle size distribution measuring apparatus. The measurement of the particle size is carried out by sufficiently dispersing the powder in an aqueous medium by ultrasonic treatment or the like, and measuring the particle-degree distribution (for example, using a micro-tracking HR A (X-100) manufactured by Nikkiso Co., Ltd.). Further, in the present specification, the above average particle diameter is referred to as an average particle diameter (D50) or D50. Further, D10 indicates the particle diameter at the point where the cumulative curve is 10%, and D90 indicates the particle diameter at the point where the cumulative curve is 90%. A method of producing a positive electrode for a lithium secondary battery using the positive electrode active material of the present invention can be carried out in a usual manner. For example, a carbon-based conductive material such as acetylene black, black lead or kitchen black is mixed with the powder of the positive electrode active material of the present invention, and mixed with a bonding material to form a positive electrode mixture. Among the above bonding materials, polyfluorinated vinylidene, polytetrafluoroethylene, polyamine, carboxymethylcellulose, acrylic resin or the like is preferably used. The slurry of the above-mentioned positive electrode mixture is dispersed in a dispersion medium such as N-methylpyrrolidone, and coated, dried, and pressure-rolled on a positive electrode current collector such as aluminum foil to form a positive electrode active material layer on the positive electrode current collector. In the lithium secondary battery using the positive electrode active material of the present invention as a positive electrode, the electrolyte contained in the battery or the electrolyte contained in the polymer electrolyte is such that one or more selected from the group consisting of C104_, CF3SO3-, BF4, and PF6- are used in -19-200818581. As the anion lithium salt, AsF6·, SbF6_, CF3C02_'(CF3S02)2N_ or the like is preferable. An electrolyte solution or a polymer electrolyte of the battery, which contains 0 in a solvent or a solvent-containing polymer. 2~2. An electrolyte composed of the above lithium salt at a concentration of 0 mol/L is preferred. When it is out of this range, the ion conductivity is lowered and the electrical conductivity of the electrolyte is lowered. More preferably, it is selected from 0. 5~1. 5 mol / L. The separator is preferably a porous polyethylene or a porous polypropylene film. Further, the solvent of the electrolyte solution is preferably a carbonate. The carbonate can be used in a ring shape or a chain shape. A cyclic carbonate such as propylene carbonate, ethylene carbonate (EC) or the like. A chain carbonate such as dimethyl carbonate, diethyl carbonate (DEC), ethyl methyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate or the like. These carbonates may be used singly or in combination of two or more. It can also be mixed with other solvents. Further, depending on the material of the negative electrode active material, when the chain carbonate and the cyclic carbonate are used, the discharge characteristics, the charge and discharge cycle characteristics, and the charge and discharge efficiency can be improved. In addition, a fluorinated ethylene-hexafluoropropylene copolymer may be added to the organic solvent (for example, Aaron Kem (trans)), fluorinated ethylene-perfluoro A propyl vinyl ether copolymer was added with the following solute as a gel polymer electrolyte. The negative electrode active material of the lithium battery using the positive electrode active material of the present invention as a positive electrode is a material capable of occluding and releasing lithium ions. The material for forming the negative electrode active material is not particularly limited, and examples thereof include lithium metal, lithium alloy, carbon material, carbon compound, carbon ruthenium compound, ruthenium oxide compound, vulcanization -20 - 200818581 titanium, boron carbide compound, and periodic table 14 The metal of Group 15 is used as the oxide of the main body. The carbon material can be used to thermally decompose organic matter under various thermal decomposition conditions, or artificial black lead, natural black lead, soil black lead, expanded black lead, scaly black lead, and the like. Further, as the oxide, a compound mainly composed of tin oxide can be used. As the negative electrode current collecting system, copper foil, nickel foil, or the like is used. The shape of the lithium secondary battery using the positive electrode active material of the present invention is not particularly limited. Depending on the application, a sheet shape (ie, a film shape), a folded shape, a rolled back type bottomed cylindrical shape, a button shape, and the like are selected. [Embodiment] The present invention will be specifically described below, but the present invention is not limited by the examples and explained. Examples 1 to 3, 6, 6, 8, 10, 12, 14 and 16 are examples of the present invention, and Examples 4, 5, 7, 7, 9, 1 and 13 Examples 1 5 and 17 are comparative examples. [Examples] [Example 1] A sulfate aqueous solution containing nickel sulfate, cobalt sulfate and manganese sulfate, an aqueous ammonium sulfate solution, and an aqueous sodium hydroxide solution were used to adjust the pH of the slurry in the reaction tank to 11 · 0, and the temperature was Stirring was carried out at 50 ° C and each was continuously supplied to the reaction tank. The amount of liquid in the reaction system was adjusted by an excessive flow reaction, and the excessively flowing coprecipitated slurry was filtered, washed with water, and then dried at 8 Torr to obtain a nickel-cobalt-manganese composite hydroxide powder. -21 - 200818581 Next, by dispersing the composite hydroxide powder in a 6% by weight aqueous solution of sodium persulfate containing 3% by weight of sodium hydroxide, stirring at 20 ° C for 12 hours to synthesize nickel-cobalt-manganese composite A carbonyl hydroxide slurry. Further, the composite carbonyl hydroxide slurry is filtered, washed with water, and then dried to obtain a composite carbonyl hydroxide powder having a specific surface area of 9. 6 m2 / g, the average particle size is 1〇. 101!1. In the obtained composite carbonyl hydroxide powder, lithium carbonate powder having a uniform φ average particle diameter of 20 μm was mixed and fired at 1 000 ° C for 16 hours in an atmosphere having an oxygen concentration of 40% by volume. From the pulverization, a base material composed of a lithium-containing composite oxide having a composition of LimXNimComMnwOmO; When the powder X-ray diffraction spectrum using the CuKa line was measured for the base material, it was found to be a structure similar to the rhombohedral system (R-3m). Further, the measurement system was a RINT 2100 model manufactured by Rigaku Corporation. When the particles of the base material powder were observed by SEM, it was found that a plurality of primary particles agglomerated to form secondary particles, and the shape thereof was approximately spherical or elliptical. • Then, in 〇. 61g titanium content is 8. 2% by weight of aqueous titanium lactate solution was added to 49. 3 9g water, modulating pH 値2. 1 Ti aqueous solution. The above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 * hours to prepare a titanium complex impregnated particles. The dried coordinating compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, and the average particle diameter is 1 〇. 3μηι, D10 is 5. 2μιη, D90 is 14. 3μιη, specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 5 m 2 /g. -22-200818581 The obtained surface-modified lithium-containing composite oxide particles were subjected to a X-ray diffraction spectrum using a ray diffraction apparatus (RINT 2100, manufactured by Rigaku Corporation). In the X-ray diffraction using the powder of the CuKa line, the diffraction peak width of the (110) plane of 2Θ = 65·1±1° is 〇·225°. The pressed density of the particles is 2. 7g/cm3. Further, the titanium contained in the entire surface of the surface-modified lithium-containing chemical particles has an atomic ratio of 0 to the total amount of nickel, manganese and cobalt. 0 0 1. With respect to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XP S analysis, (Ti/N) = 0. 7 1. In addition, the amount of lithium ion elution is 0. 2 1 mole %. The surface-modified lithium-containing composite oxide particles are mixed with acetylene fluorene and polyfluorinated vinylidene powder in a weight ratio of 90/5/5, and N-methylpyrrolidone is added to prepare a slurry, and the aluminum foil having a thickness of 20 μ? Apply a single side with a spatula. A positive electrode sheet for a lithium battery was produced by drying and rolling and rolling three times. Then, the above-mentioned positive electrode body sheet was used as a positive electrode through a perforator, a metal lithium foil having a thickness of 500 μm was used as a negative electrode, a 20 μm nickel foil was used as a negative electrode current collector, and a porous polypropylene having a thickness of 25 μm was used as a separator, and used. A solution of LiPF6/EC + DEC (1:1) at a concentration of 1 ( (refers to a mixed solution of EC to DEC by a ratio of 1^1^6 as a solute. The following solvents are also used as such Benchmark.) As an electrolyte, four stainless steel simple sealed cell type lithium batteries were assembled in an argon small toolbox. With respect to the above one battery, 1 g of the positive electrode active material was charged to 4 · 3 V at a load current of -23-200818581 3 0 m A at 25 ° C, and 1 g of the positive electrode active material was discharged to 3 〇 11 八 load current to 2 . 5 V ' to obtain the initial discharge capacity. Further, regarding the battery, a charge and discharge cycle test was performed 30 times. The result is in 25 art, 2. 5 ~ 4. The initial weight capacity density of the positive active material of 3 V was 159 m Ah/g, and the capacity retention rate after 30 charge and discharge cycles was 98. 5%. In addition, regarding a battery, in addition to making the charging voltage from 4. 3V was changed to 4. 5V, 25 times of charge and discharge cycle test, the result of the same operation, 2. 5~4. The initial weight capacity density of the positive electrode active material of 5 V was 175 m Ah/g, and the capacity retention rate after the 25 charge and discharge cycles was 94. 9%. In addition, regarding the other battery system, each has 4. 3 V and 4. 5 V was charged for 10 hours, disassembled in a small argon gas kit, and the charged positive electrode sheet was taken out, and the positive electrode sheet was washed, perforated to a diameter of 3 mm, and sealed in an EC and aluminum capsule, and The temperature was raised at a rate of 5 ° C /min using a scanning differential calorimeter, and the heat start temperature was measured. As a result, 4. The heating start temperature of the heating curve of the 3V charging product is 233 °C, 4. The 5 V charger is 198 °C. [Example 2] As in the case of Example 1, the synthetic base material has Lii. 02(Nii/3C〇i/3Mni/3)0. A lithium-containing composite oxide composed of 98〇2. Then, at 3. 03g titanium content is 8. 2% by weight of aqueous titanium lactate solution is added to 4. 9 7 g of water was prepared to prepare a T i aqueous solution of p Η値2. 100 g of the above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 - 24 to 2008 18581 hours to prepare a titanium complex impregnated particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, and the average particle diameter is 1 〇 · 5 μιη, D 1 0 is 5 · 5 μπι, and D9 0 is 14 ·6μπι, specific surface area is 〇. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 5 m 2 /g. - The obtained surface-modified lithium-containing composite oxide particles were measured for the X-ray diffraction spectrum in the same manner as in Example 1. Powder X-ray diffraction using CuKa line • Medium, 2Θ = 65·1 Soil 1. The diffraction peak width of the (110) plane is 0. 226. . The pressed density of the particles is 2. 69g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 0 0 5. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) =1. 50. In addition, the amount of lithium ion elution is 0. 29 moles %. # As described above, in the IR spectrum of Fig. 1, since there is a strong absorption peak in the range of 1 3 00 to 1 700 CHT1, it is known that the surface layer of the surface-modified lithium composite oxide has carbon- A carbon compound having an oxygen double bond is present. Further, as is apparent from Fig. 2, the titanium lactate was subjected to a decomposition reaction at 300 to 45 ° C, and the decomposition reaction was almost completed at 500 °C. In addition, in the surface layer of the surface-modified lithium-containing composite oxide particles synthesized by heat treatment at 3 50 ° C in Example 2, a carbon compound was present. Further, it is understood that a partial thermal decomposition product of a carbon-containing titanium complex compound using a carbon compound as a raw material of -25 - 200818581 is used. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2 · 5 ~ 4. The initial weight capacity density of the positive active material of 3 V was 159 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 8. 3 %. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 175 mAh/g, and the capacity retention rate after 25 charge and discharge cycles was 9 5. 1 %. Further, the temperature was raised at a rate of 5 ° C /min using a scanning differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 23 5 °C, 4. The heating start temperature of the 5V charging product is 200 〇C. [Example 3] Φ In the same manner as in Example 1, a lithium-containing composite oxide having a composition of a base material was synthesized. Then, the titanium content at 6 · 0 5 g is 8. 2% by weight of aqueous lactate solution was added to 43. 95 g of water was prepared to prepare a Ti aqueous solution of pH 値2. The above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordinating compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, and the average particle diameter is 10. 7μιη, D10 is 6. 1μπι, D90 is -26- 200818581 15·〇μιη, specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 5 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKa line, the diffraction peak width of the (110) plane of 2Θ = 65·1±Γ is 0. 230. . The pressed density of the particles is 2. 69g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 01. In addition to the above-mentioned τ, the obtained surface-modified lithium-containing composite oxide particles were measured for the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles by XPS analysis in the same manner as in Example 1 (Ti /N) =3. 30. In addition, the amount of lithium ion elution is 0. 38 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2 · 5 ~ 4. The initial weight capacity density of the 3V positive electrode active material was 157 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 98. 2%. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 173 mAh/g, and the capacity retention rate after performing 25 charge and discharge cycles was 95. 1%. In addition, the temperature of the heating start temperature was measured by a scanning differential calorimeter at a rate of 5 ° C / min. The heating start temperature of the 3 V charging product is 234 ° C, 4. The heating start temperature of the 5V rechargeable product is 2 01〇C. -27- 200818581 [Example 4] In the same manner as in Example 1, the synthetic base material has LiuHNimComMm/Do. A lithium-containing composite oxide composed of MC^. The base material has an average particle size of 1 〇. 5 μιη and D10 are 5. 3μιη, D90 is 1 3. 5 μιη, specific surface area is 0. 4 9 m2 / g of the primary particles are mostly agglomerated and formed into particles of secondary particles. About the composite oxide particles, an X-ray diffraction spectrum was prepared using an X-ray diffraction apparatus (RINT 2100, manufactured by Rigaku Corporation). In the powder X-ray diffraction using the CuKa line, the diffraction peak width of the (110) plane of 2Θ = 65·1 soil 1° is 0. 225°. The pressed density of the particles is 2. 70g/cm3. Further, in the case of the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Further, as described above, in the IR spectrum of Fig. 1, since the absorption peak is strong in the range of 1 3 00 to 1 700 CHT1, it is understood that the composite oxide of lithium is free of carbon having a carbon-oxygen double bond. Compound. Using a lithium-containing composite oxide particle of a base material, a positive electrode sheet was produced in the same manner as in Example 1, and a battery was assembled for evaluation. As a result, the initial weight capacity density of the positive electrode active material at 25 ° C and 2 · 5 to 4 · 3 V was 160 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 5. 0%. Further, the initial weight capacity density of the positive electrode active material at 25 ° C and 2 · 5 to 4 · 5 V was 1 75 mAh/g, and the capacity retention rate after performing 25 charge and discharge cycles was 9 1. 0%. -28- 200818581 In addition, the temperature of the heating start temperature was measured by a scanning differential calorimeter at a rate of 5 ° C / min. The heating start temperature of the 3V charging product is 232 ° C, 4. The heating start temperature of the 5V rechargeable product is 199 〇C 〔 [Example 5] Same as Example 1 "The synthetic base material has Lii. G2 (Nii/3C〇i/3Mni/3) G. A lithium-containing composite oxide composed of 98〇2. Then, in 〇. 〇6g titanium content is 8. 2% by weight of aqueous titanium lactate solution was added to 49. 94g water, modulation! )11値2. 5 of 14 aqueous solution. The above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 1, 20 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordination compound impregnated particles were heated in an oxygen-containing gas atmosphere at 3 50 ° C for 12 hours, and the average particle diameter was 10. 4μιη, D10 is 5. 0μηι, D90 is 14. 1μιη, specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 48 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKa line, 2Θ = 65. 1 士 1. The diffraction peak width of the (110) plane is 0. 224. . The pressed density of the particles is 2. 70g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 0 0 0 1. Further, in the case of the obtained surface-modified lithium-containing composite oxide particles, -29-200818581, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles is measured by XPS analysis in the same manner as in Example 1, (Ti/N ) =0. 18. In addition, the amount of lithium ion elution is 0. 20 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. ‘ Result, at 25°c, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 160 mAh/g, and the capacity after the 30 charge and discharge cycles was maintained at φ rate of 9. 2 %. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 173 mAh/g, and the capacity retention rate after the charge and discharge cycle of 25 times was 91. 2%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3 V charging product is 234 ° C, 4. The heating start temperature of the 5V rechargeable product is 201 °C ° [Example 6] 197. The average particle size of 18g is 12. ; ^ 111, cobalt content is 61. 0% by weight of cobalt hydroxide, 〇·16 g of aluminum hydroxide, 〇·1 2 g of magnesium hydroxide, mixed with '75·91§ lithium carbonate powder having a specific surface area of I2m2/g, in an oxygen-containing gas environment After firing at 990 ° C for 14 hours, it was prepared by disintegration to obtain LUCoojw AluHMg. (4) A base material composed of a lithium-containing composite oxide composed of 1). Then 'in the 〇. 〇6g titanium content is 8. 2% by weight of aqueous titanium lactate -30- 200818581 50 g of water was added to prepare a Ti aqueous solution of pH 値2.5. One 〇〇g of the above-mentioned base material was immersed in the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particle. The dried coordination compound impregnated particles were heated in an oxygen-containing gas atmosphere at 3 50 ° C for 12 hours, and the average particle diameter was 12·0 μιη, and D10 was 6. 7μπι, D90 is 18·8μχη, and the specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 25 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKa line, 2Θ = 66. 5±1. The diffraction peak width of the (110) plane is 0. 108. . The pressed density of the particles is 3. 0 2 g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 0 0 1. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) =1. 26. In addition, the amount of lithium ion elution is 0. 09 mole%. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 157 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 99. 8%. In addition, at 25 ° C, 2. 5~4. The initial weight of the positive active material of 5V is 200818581. The capacity density is 184mAh/g, and the capacity retention rate after performing 25 charge and discharge cycles is 97. 0%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating temperature of the 3V charging product has a heating start temperature of 158 ° C, 4. The heating start temperature of the 5V rechargeable product is 146 〇 C ° [Example 7] Make 1 96. The average particle size of 99g is 12. Ιμηι, cobalt content is 61. 0% by weight of cobalt hydroxide, 0. 1 6g aluminum hydroxide, 0. 12g magnesium hydroxide, and 〇. 16g titanium oxide, 75. 91g specific surface area is 1. 2m2/g of lithium carbonate powder is mixed and fired in an oxygen-containing gas atmosphere at 990 °C for 14 hours, and then obtained by containing Li(C〇〇. 997Al〇. 〇〇iMg(). 〇()iTi〇. 含i) A lithium-containing composite oxide composed of 〇2. The lithium-containing composite oxide has an average particle diameter of 1 〇. 3μιη, D10 is 6. 4μιη, D90 is 1 5 · 4μπι, and the specific surface area is 0. About 26 m 2 /g of a spherical shape X The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. Use the powder of the CuKot line. In the X-ray diffraction, the width of the diffraction peak of the (110) plane is 2Θ = 66·5. 097. . The pressed density of the particles is 3. 0 9 g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing material particles has an atomic ratio of 0 to a total amount of cobalt, aluminum, magnesium, and titanium. 001. Further, in the case of the obtained surface-modified lithium-containing composite oxide particles, -32-200818581, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N ) =0. 15. In addition, the amount of lithium ion elution is 0. 1 0% by mole. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. * The result is at 2 5 °C, 2 · 5~4. The initial weight capacity density of the positive electrode active material of 3 V was 159 mAh/g, and the capacity after the 30 charge and discharge cycles was maintained at φ rate of 9 6 · 9 %. In addition, at 2 5 °C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 185 mAli/g, and the capacity retention rate after 25 charge and discharge cycles was 8 3. 0%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product is 1S5°C, 4. The heating start temperature of the 5V rechargeable product is 145 〇C. [Example 8] At 51. In the water of 03g, 1. 20 g of magnesium hydroxide was dispersed, stirred, and dissolved in a small amount of 5 · 4 6 g of citric acid. Then, join 1 2. 3 1 g of a 4 % by weight aluminum aluminum lactate aqueous solution was mixed to prepare an aqueous solution (Al-Mg solution) containing aluminum and magnesium. Make 1 96. 62g average particle size is 12·0μχη, and the content of Ming is 60. In the case of the above-mentioned A1 - M g, it is easy to carry out impregnation and mixing, and drying at 120 ° C for 4 hours to obtain a carbonyl-33-200818581 cobalt hydroxide powder containing aluminum and magnesium. By making 77. 72g specific surface area is 1. 2 m 2 /g of lithium carbonate powder was mixed with the above-mentioned aluminum and magnesium cobalt oxyhydroxide powder, and fired in an oxygen-containing gas atmosphere at 990 ° C for 14 hours, and then pulverized to obtain Lil. G2 (C〇G. 98Al〇. 〇lMg〇 ()l)G. A block-shaped composite oxide having a composition of 98 〇 2 is used as a base material. Then, in 〇. Add 6g of water to 6g of magnesium hydroxide, stir and add a small amount of bismuth. 14 g of citric acid was dissolved. Then, join 0. 06g titanium contains - the amount is 8. 2% by weight of an aqueous solution of titanium lactate, adjusted to pH 値 2. An aqueous solution containing magnesium and titanium (Mg-Ti aqueous solution). After 100 g of the above-mentioned base material was immersed in the above Mg-Ti aqueous solution, it was slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a magnesium-titanium complex compound impregnated particles. The dried coordination compound impregnated particles were heated in an oxygen-containing gas atmosphere at 40 ° C for 12 hours, and the average particle diameter was 12·6 μιη, and D10 was 6. 8μιη, D90 is 19·0μιη, and the specific surface area is 0. About 30 m 2 /g of a spherical composite oxide particle containing surface-modified lithium. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKa line, 2Θ = 6 6. 5 The radius of the diffraction peak of the (110) plane is 0. 108. . The pressed density of the particles is 3. 03 g/cm3. Further, the magnesium and titanium contained in the entire surface-modified lithium-containing material particles have an atomic ratio of 0 to a total of cobalt, aluminum and magnesium. 002. Further, the titanium contained in the entire composite oxide particles containing surface-modified lithium is -34-200818581 W in a total amount of cobalt, aluminum and magnesium, and the atomic ratio is 0. 0 0 1. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) = 1 · 1 7. In addition, the amount of lithium ion elution is 0. 20 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 151 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 9. 5 %. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 178 mAh/g, and the capacity retention rate after 25 charge and discharge cycles was 9. 2 %. In addition, the temperature was raised at a rate of 5 ° C /min using a scanning differential calorimeter, and the result of the heat start temperature was measured. The heating temperature of the 3V charging product has a heating start temperature of 159 ° C, 4. The heating start temperature of the 5V rechargeable product is 147〇C. [Example 9] 0 in 50 g of water. 06g of magnesium hydroxide was dispersed, stirred and added to each other in a small amount of 0. 14 g of citric acid was dissolved, and the pH was adjusted to 4. 0 mg of water solution. By making l〇〇g the Lii synthesized in Example 8. G2 (C〇Q. 98AlG, () iMg〇. ()i)(). The lithium-containing composite oxide having a composition of 98 Å was immersed in the above Mg aqueous solution, and slowly mixed at a slow -35 - 200818581 to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a magnesium complex impregnated particles. The dried coordination compound impregnated particles were heated in an oxygen-containing gas atmosphere at 400 ° C for 12 hours, and the average particle diameter was 11.8 μm and D10 was 6. 6μιη, D90 ' is 17·8μπι, and the specific surface area is 〇. A spherical surface repair of 23 m2/g. A composite oxide particle decorated with lithium. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1 φ. Using the powder X-ray diffraction of the CuKa line, 20 = 66. 5 士1. The diffraction peak width of the (110) plane is 0. 10-4. . The pressed density of the particles is 3. 06g/cm3. Further, the magnesium contained in the entire surface-modified lithium-containing material particles has an atomic ratio of 0 for cobalt. 001 〇 In addition, the obtained surface-modified lithium-containing composite oxide particles were not detected in the surface element analysis by XPS analysis in the same manner as in Example 1. Moreover, the amount of lithium ion elution is 0. 24 moles %. • The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the 3V positive active material was 15 ImAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 9. 0%. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 1 80 m Ah/g, and the capacity retention rate after 25 charge and discharge cycles was 9 2. 5 %. In addition, the temperature of the starting temperature of the heat was measured by a scanning differential calorimeter at a rate of 5 ° C / min. The heating temperature of the 3V charging product has a heating start temperature of 154 ° C, 4. The heat generation start temperature of the 5V charge product was 144 ° C ° [Example 10] The lithium carbonate powder was mixed in a predetermined amount in the composite carbonyl hydroxide powder obtained in Example 1, and fired and pulverized in the same manner as in Example 1. A lithium-containing composite oxide having a composition of a synthetic base material. Then, in 〇. 61g titanium content is 8. 2% by weight of aqueous titanium lactate solution was added to 49. 3 9g water, modulating pH 値2. 1 Ti aqueous solution. 100 g of the above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 40 ° C for 12 hours, and the average particle diameter is ΙΙ. Ομηι, D10 is 6. 3μηι, D90 is 15·5μιη, and the specific surface area is 0. The composite oxide particles of the surface-modified lithium of the present invention having a spherical shape of about 49 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. Using the powder X-ray diffraction of the CuKa line, 20 = 65. 1 soil 1. The diffraction peak width of the (110) plane is 0. 199. . The pressed density of the particles is 2. 67g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing material particles has an atomic ratio of 〇· 〇 〇 1 for the total amount of nickel, manganese and cobalt. Further, in the case of the obtained surface-modified lithium-containing composite oxide particles, the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by xps analysis in the same manner as in Example 1. (Ti/N) = 〇·7. In addition, the amount of lithium ion elution is 0. 38 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 2 5 °C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 157 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 8. 5 %. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 173 mAh/g, and the capacity retention rate after the 25 charge and discharge cycles was 94. 5%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 231 °C, 4. The heating start temperature of the 5V charge product was 200 °C. [Example 11] A lithium-containing composite oxide having a composition of the base material was synthesized in the same manner as in Example 10. The average particle size of the base metal is 10. 8 μπι, D10 is 6·1μπι, and D90 is 1 5 . 1 μηι, specific surface area is 0. A powder of a primary particle of 47 m 2 /g which is mostly agglomerated and forms a secondary particle. About the composite oxide particles, an X-ray diffraction spectrum was prepared using an X-ray diffraction apparatus (RINT 2100, manufactured by Rigaku Corporation). In the powder X-ray diffraction of CuKa -38- 200818581 line, the diffraction wavelength of the (110) plane of the 2Θ = 65·1 soil is half the width of the peak. 197°. The pressed density of the particles is 2. 70g/cm3. Further, in the case of the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Using the lithium-containing composite oxide particles of the above-mentioned base material, a positive electrode was prepared in the same manner as in Example 1, and a battery was assembled and evaluated. As a result, at 2 5 °C, 2. The initial weight capacity density of the positive electrode active material of 5 to 4 · 3 V was 1 59 nrAh/g, and the capacity retention rate after 30 charge and discharge cycles was 94. 9%. In addition, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 5 V was 174 mAh/g, and the capacity retention rate after 25 charge and discharge cycles was 90. 0%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product is 23 0 ° C, and the heating start temperature of the 4·5 V charging product is 198 ° C ° [Example 1 2] The ratio of each element containing nickel, cobalt and manganese is adjusted to NkC. (KMn = 0. 50:0. 20:0. The nickel sulfate of 30 is mixed with the sulfate of cobalt sulfate and manganese sulfate. The aqueous solution, the aqueous solution of ammonium sulfate and the aqueous sodium hydroxide solution are used to make the pH of the slurry in the reaction tank to be 11. 0, stirring was carried out at a temperature of 50 ° C and each was continuously supplied to the reaction tank. The amount of liquid in the reaction system was adjusted by an excessive flow method, and the coprecipitated slurry flowing through -39 - 200818581 was filtered, washed with water, and then dried at 80 ° C to obtain a nickel-cobalt-manganese composite hydroxide powder. . Next, the nickel-cobalt-manganese composite carbonyl hydroxide slurry was synthesized by dispersing the composite hydroxide powder in a 6% by weight aqueous sodium persulfate solution containing 3% by weight of sodium hydroxide and stirring at 20 ° C for 12 hours. . Further, the composite carbonyl hydroxide slurry was filtered, washed with water, and then dried to obtain a composite carbonyl hydroxide powder. The composite carbonyl hydroxide powder has a specific surface area of 9. 4m2 / g, the average particle size is 9. 5μπι. The lithium carbonate powder having an average particle diameter of 20 μm was mixed in the composite carbonyl hydroxide powder thus obtained, and calcined in an oxygen-containing gas atmosphere at 970 ° C for 12 hours, and then pulverized. It is made to contain Lh. oKNio. sCoo. iMno. Oo. A base material composed of a lithium-containing composite oxide composed of ^C^. Regarding the base material, when the powder was further measured by the CuKa line and the diffraction spectrum of the powder, it was found to be a similar structure of the surface system (R-3m). Further, the RINT 2 100 model manufactured by Rigaku Corporation was used for the measurement. Regarding the particles of the base material powder, when the SEM observation is performed, most of the primary particles agglomerate to form secondary particles, and the shape thereof is approximately spherical or elliptical. Second, then, in 〇. 60g titanium content is 8. 2% by weight of titanium lactate aqueous solution was added 49. 40g water, modulating pH値2. 1 Ti aqueous solution. The above base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, the average particle diameter is 9·2 μπι, D10 is 5·2 μιη, and D90 is -40-200818581 15· 0μιη, specific surface area is 0. The composite oxide particles of the surface-modified lithium of the present invention having a spherical shape of about 52 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CuKoi line, 2Θ = 65. The diffraction peak width of the (±1) (110) plane is 0. 13 9. . The pressed density of the particles is 2. 65g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 001. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) =0. 69. In addition, the amount of lithium ion elution is 0. 59 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the 3V positive electrode active material was 165 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9.7 5%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product is 2〇2°C. [Example 1 3] In the same manner as in Example 12, the synthetic base material had Lii. Gi (NiG. 5C〇G. 2Mn(). 3) (). A lithium-containing composite oxide composed of 99〇2. The average particle size of the base metal is 8. 9Pm, -41 - 200818581 D10 is 5. A powder of 0 μιη, D90 of 1 4 · 9 μιη, and a specific surface area of Ο · 50 m 2 /g, in which primary particles are mostly agglomerated and particles of secondary particles are formed. With respect to the composite oxide particles, an X-ray diffraction spectrum was obtained using an X-ray diffraction apparatus (RINT 2 100 manufactured by Rigaku Corporation). In the powder X-ray diffraction using the CuKa line, 2Θ = 65. The diffraction peak of the (1) ( (110) plane has a half-turn width of 0. 135°. The pressed density of the particles is 2. 69g/cm3. Further, in the case of the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Using the lithium-containing composite oxide particles of the above-mentioned base material, a positive electrode body was produced in the same manner as in Example 1, and a battery was assembled and evaluated. As a result, at 25 ° C, 2 · 5 ~ 4. The initial weight capacity density of the positive active material of 3 V was 168 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 6. 0%. In addition, the temperature of the heating start temperature was measured by a scanning differential calorimeter at a rate of 5 ° C / min. The heat generation curve of the 3 V charging product has a heating start temperature of 201 °C. [Example 1 4] The ratio of each element containing nickel, cobalt and manganese is adjusted to Ni: Co: Mn = 03 5:0. 40:0. 25 aqueous solution of nickel sulfate and cobalt sulfate and manganese sulfate mixed with water, ammonium sulfate aqueous solution and aqueous sodium hydroxide solution, so that the pH of the slurry in the reaction tank is 11. 0. The temperature was 50 ° C and the mixture was continuously supplied to the reaction tank. The amount of liquid in the reaction system was adjusted by an excessive flow method, and the coprecipitated slurry flowing in excess of -42 - 200818581 was filtered, washed with water, and then dried at 80 ° C to obtain a nickel-cobalt-manganese composite hydroxide powder. Next, the nickel-cobalt-manganese composite carbonyl hydroxide slurry was synthesized by dispersing the composite hydroxide powder in a 6% by weight aqueous solution of sodium persulfate containing 3% by weight of sodium hydroxide and stirring at 20 ° C for 12 hours. material. Further, the composite carbonyl hydroxide slurry was filtered, washed with water, and then dried to obtain a composite carbonyl hydroxide powder. The composite carbonyl hydroxide powder has a specific surface area of 9. 4m2 / g, the average particle size is 9. 5μπι. The lithium carbonate powder having an average particle diameter of 20 μm was mixed in the composite carbonyl hydroxide powder thus obtained, and calcined in an oxygen-containing gas atmosphere at 990 ° C for 12 hours, and then pulverized. It is made of LiKNimCOo. 4 (^11(). 25) (). A base material composed of a lithium-containing composite oxide composed of 9902. Regarding the base material, when the powder X-ray diffraction spectrum was measured using a CuKa line, it was found to be a similar structure of the surface system (R-3m). Further, RINT 2 00 type manufactured by Rigaku Electric Co., Ltd. was used for the measurement. When the particles of the base material powder are observed by SEM, most of the primary particles are agglomerated to form secondary particles, and the shape thereof is approximately spherical or elliptical. Second, then, in 〇. 60g titanium content is 8. 2 wt% of titanium lactate aqueous solution was added 49. 40 g of water to prepare pH 値 2. 1 Ti aqueous solution. The mixed powder was prepared by immersing the above-mentioned base material in 5 (1 of the above aqueous solution), and then mixing the mixture to prepare a mixed powder at 120 ° C for 4 hours to obtain a titanium compound. The compound is impregnated with particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, and the average particle size is ΙΟ. Ιμηι, D10 is 5. 0μπι, D90 -43- 200818581 is 14·1μπι, and the specific surface area is 0. The surface-modified lithium composite oxide particles of the present invention having a spherical shape of about 46 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. In the powder X-ray diffraction using the CiiKa line, the diffraction peak width of the (110) plane of 2Θ = 65·1±Γ is 0. twenty two. . The pressed density of the particles is 2. 72g/cm3. Further, the titanium contained in the entire surface-modified lithium-containing compound particles has an atomic ratio of 0 to a total of nickel, manganese and cobalt. 0 0 1. Further, in relation to the obtained surface-modified lithium-containing composite oxide particles, when the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles was measured by XPS analysis in the same manner as in Example 1, (Ti/N) ) =0·72. In addition, the amount of lithium ion elution is 0. 35 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the 3V positive electrode active material was 153 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9.7 3%. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 1 9 1 °C. [Example 1 5] In the same manner as in Example 14, the synthetic base material had Lii. oKNio. A lithium-containing composite oxide composed of hCocMoMnuOGMCb. The average particle size of the base material is 9·9 μηι, -44- 200818581 D10 is 4·9 μπι, D90 is 13·9 μπι, and the specific surface area is 0. A powder of a primary particle of 40 m 2 /g which is mostly agglomerated and forms a secondary particle. With respect to the composite oxide particles, an X-ray diffraction spectrum was prepared using an X-ray diffraction apparatus (RINT 2100 manufactured by Rigaku Corporation). In the powder X-ray diffraction using the CuKa line, 2 Θ = 65·1 ± 1. The diffraction peak of the (110) plane has a half-turn width of 0. 219°. The pressed density of the particles is 2. 75g/cm3. Further, in the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Using the lithium-containing composite oxide particles of the above-mentioned base material, a positive electrode body was produced in the same manner as in Example 1, and a battery was assembled and evaluated. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 155 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 6. 0%. In addition, the temperature was raised by a scanning differential calorimeter at a rate of 5 t:/min, and the result of the heat start temperature was measured. The heat generation curve of the 3V charging product has a heating start temperature of 190 °C. [Example 1 6] The ratio of each element containing nickel, Ming and 锸 is adjusted to N i: C 〇 : Μ η = 〇·3 0:0. 30:0. The nickel sulfate of 40 is mixed with the sulfate of cobalt sulfate and manganese sulfate. The aqueous solution, the aqueous solution of ammonium sulfate and the aqueous solution of sodium hydroxide are used to make the slurry of the slurry in the reaction tank 1 . 0, the temperature was stirred at 5 ° C and each was continuously supplied to the reaction tank. The amount of liquid in the reaction system was adjusted by excessive flow, and the coprecipitated slurry flowing through -45-200818581 was filtered, washed with water, and then dried at 8 〇t: to obtain nickel-cobalt-manganese composite hydroxide. powder. Next, the nickel-cobalt-manganese composite carbonyl hydroxide was synthesized by dispersing the composite hydroxide powder in a 6% by weight aqueous solution of sodium persulfate containing 3% by weight of sodium hydroxide and stirring at 20 ° C for 12 hours. Slurry. Further, the composite carbonyl hydroxide slurry was filtered, washed with water, and then dried to obtain a composite carbonyl hydroxide powder. The composite carbonyl hydroxide powder has a specific surface area of l〇. 8m2 / g, the average particle size is 9. 0μπι. The lithium carbonate powder having an average particle diameter of 20 μm was mixed in the composite carbonyl hydroxide powder thus obtained, and calcined in an oxygen-containing gas atmosphere at 95 ° C for 12 hours, and then pulverized. A base material composed of a lithium-containing composite oxide having a composition is prepared. Regarding the base material, when the powder X-ray diffraction spectrum was measured using a CxiKa line, it was found to be a similar structure of the surface system (R-3m). Further, the RINT 2100 model manufactured by Rigaku Corporation was used for the measurement. When the particles of the base material powder were observed by SEM, most of the primary particles agglomerated into secondary particles, and the shape thereof was approximately spherical or elliptical. Second, then, in 〇. 61g titanium content is 8. 2% by weight of titanium lactate aqueous solution was added 49. 3 9 g of water, and a Ti aqueous solution of pH 値 2·1 was prepared. 100 g of the above-mentioned base material was immersed in 50 g of the above Ti aqueous solution, and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C for 4 hours to obtain a titanium complex impregnated particles. The dried coordination compound impregnated particles are heated in an oxygen-containing gas atmosphere at 350 ° C for 12 hours, the average particle diameter is 9·0 μπι, D10 is 4·5 μπι, and D90 is -46-200818581 14 . 8μπι, specific surface area is 〇. The composite oxide particles of the surface-modified lithium of the present invention having a spherical shape of about 65 m 2 /g. The X-ray diffraction spectrum of the obtained surface-modified lithium-containing composite oxide particles was measured in the same manner as in Example 1. Using the powder X-ray diffraction of the CuKa line, 20 = 65. The diffraction peak width of the 1±1° (11〇) plane is 〇. 272°. The pressed density of the particles is 2. 5 1 g/cm3. Further, the yttrium contained in the entire surface of the surface-modified lithium-containing compound particles has an atomic ratio of 0 for nickel, manganese, and mineralization. 00 1. Further, the obtained surface-modified lithium-containing composite oxide particles t were measured for the atomic ratio (Ti/N) of the surface of the lithium-containing composite oxide particles by XPS analysis in the same manner as in Example 1, (Ti/N). ) =0. 70. In addition, the amount of lithium ion elution is 0. 3 7 moles %. The positive electrode sheet was prepared and evaluated in the same manner as in Example 1 except that the composite oxide containing the surface-modified lithium was used. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the 3V positive active material was 140 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9 7. 8 %. Further, the temperature was raised at a rate of 5 ° C /min by a scanning type differential calorimeter, and the result of the heat generation start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 240 °C. [Example 1 7] • In the same manner as in Example 16, the synthetic base material has Lii. 〇l (Ni〇. 3GC〇G. 3()Mn〇. 4G) G. A lithium-containing composite oxide composed of 99〇2. The base material has an average particle diameter of 8 · 5 μιη, -47-200818581 D10 of 4·5 μιη, D90 of 14·2 μιη, and a specific surface area of 〇. A powder of a primary particle of 62 m 2 /g which is mostly agglomerated and forms a secondary particle. With respect to the composite oxide particles, an X-ray diffraction spectrum was prepared using an X-ray diffraction apparatus (RINT 2100 manufactured by Rigaku Corporation). In the powder X-ray diffraction using the CuKa line, the diffraction peak of the (110) plane of 2Θ = 65·1 gΓ is half width. 27°. The pressed density of the particles is 2. 55g/cm3. Further, in the case of the lithium-containing composite oxide particles of the above-mentioned base material, when surface element analysis was carried out by XPS analysis in the same manner as in Example 1, titanium was not detected. Using the lithium-containing composite oxide particles of the above-mentioned base material, a positive electrode body was produced in the same manner as in Example 1, and a battery was assembled and evaluated. As a result, at 25 ° C, 2. 5~4. The initial weight capacity density of the positive active material of 3 V was 142 mAh/g, and the capacity retention rate after 30 charge and discharge cycles was 9.6 · 1%. In addition, the temperature was raised at a rate of 5 ° C /min using a scanning differential calorimeter, and the result of the heat start temperature was measured. The heating start temperature of the 3V charging product has a heating start temperature of 23 9 °C. [Industrial Utilization Price] According to the present invention, it is possible to provide a nonaqueous electrolyte composed of lithium-containing composite oxide particles which does not lower high safety, has high operating voltage, high discharge capacity, and excellent charge and discharge cycle characteristics. A positive electrode active material for a storage battery, a method for producing the positive electrode active material, and a nonaqueous electrolyte secondary battery using the positive electrode active material. -48- 200818581 Moreover, the application for the application No. 2006-212647 and the scope of patent application for the application of the application dated 20 06-2 03 99 3, filed on July 26, 2006, and August 3, 2006 The entire contents of the drawings and the disclosures of the present invention are applied to the disclosure of the present specification. [Fig. 1] shows the infrared absorption (IR) of the decorative lithium-containing composite oxide obtained in Example 2 (Example). ) Infrared absorption of the lithium-containing composite oxide obtained by the spectrum (A) and (Comparative Example) (spectrum (B) 〇 [_Fig. 2] shows the thermal weight differential weight of the dried titanium lactate (TG-DTA-DTG) The results of the analysis of the analysis. 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