TWI535097B - A positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery - Google Patents
A positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery Download PDFInfo
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- C01G53/00—Compounds of nickel
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- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Description
本發明係關於一種鋰離子電池用正極活性物質、鋰離子電池用正極、及鋰離子電池。 The present invention relates to a positive electrode active material for a lithium ion battery, a positive electrode for a lithium ion battery, and a lithium ion battery.
鋰離子電池之正極活性物質，通常使用含鋰之過渡金屬氧化物。具體而言，為鈷酸鋰(LiCoO2)、鎳酸鋰(LiNiO2)、錳酸鋰(LiMn2O4)等，為了改善特性(高容量化、循環特性、保存特性、降低內部電阻、比率(rate)特性)或提高安全性，而不斷對該等進行複合化。對於車輛用或負載調平(load leveling)用等大型用途中之鋰離子電池，謀求與至今為止之行動電話用或個人電腦用不同之特性。 For the positive electrode active material of a lithium ion battery, a lithium-containing transition metal oxide is usually used. Specifically, it is lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), etc., in order to improve characteristics (high capacity, cycle characteristics, storage characteristics, internal resistance reduction, Rate characteristics) or improve security, and constantly compositing them. For lithium-ion batteries in large-scale applications such as vehicles or load leveling, they are designed to have different characteristics from those used in mobile phones or personal computers.
為了改善電池特性，先前使用各種方法，例如於專利文獻1中揭示有一種下述鋰二次電池用正極材料之製造方法，其特徵在於：將LixNi1-yMyO2-δ In order to improve the battery characteristics, various methods have been previously used. For example, Patent Document 1 discloses a method for producing a positive electrode material for a lithium secondary battery, which is characterized in that Li x Ni 1-y M y O 2-δ
(0.8≦x≦1.3，0<y≦0.5，M表示選自由Co、Mn、Fe、Cr、V、Ti、Cu、Al、Ga、Bi、Sn、Zn、Mg、Ge、Nb、Ta、Be、B、Ca、Sc及Zr組成之群中的至少一種元素，δ相當於氧欠缺或氧過剩量，表示-0.1<δ<0.1)之組成所示的鋰鎳複合氧化物通過分級機，以平衡分離粒徑Dh=1~10μm分離成粒徑較大者與較小者，以重量比為0：100~100：0摻合粒徑較大者與較小者。並且，記載有若根據該方法，即可輕易製造比率特性與容量各項平衡的鋰二次 電池用正極材料。 (0.8≦x≦1.3,0<y≦0.5, M means selected from Co, Mn, Fe, Cr, V, Ti, Cu, Al, Ga, Bi, Sn, Zn, Mg, Ge, Nb, Ta, Be At least one element selected from the group consisting of B, Ca, Sc, and Zr, δ corresponds to an oxygen deficiency or an excess amount of oxygen, and the lithium nickel composite oxide represented by the composition of -0.1 < δ < 0.1) passes through a classifier to The equilibrium separation particle size Dh=1~10μm is separated into smaller and smaller particles, and the weight ratio is 0:100~100:0, and the smaller the particle size is smaller and smaller. Further, it is described that, according to the method, lithium secondary having a balance between the ratio characteristics and the capacity can be easily produced. Positive electrode material for battery.
[專利文獻1]日本專利第4175026號公報 [Patent Document 1] Japanese Patent No. 4175526
專利文獻1中記載之鋰鎳複合氧化物係其組成式中之氧量過剩者，但即便如此，對於作為高品質之鋰離子電池用正極活性物質而言，仍然具有改善之餘地。 The lithium-nickel composite oxide described in Patent Document 1 is one in which the amount of oxygen in the composition formula is excessive. However, there is still room for improvement in the high-quality positive electrode active material for lithium ion batteries.
因此，本發明之課題在於，提供一種具有良好電池特性之鋰離子電池用正極活性物質。 Therefore, an object of the present invention is to provide a positive electrode active material for a lithium ion battery having good battery characteristics.
本發明人等經潛心研究，結果發現正極活性物質之氧量與電池特性之間存在緊密之相關關係。即，發現當正極活性物質之氧量為某數值以上時，可獲得良好之電池特性。 The inventors of the present invention conducted intensive studies and found that there is a close correlation between the amount of oxygen of the positive electrode active material and the battery characteristics. That is, it was found that when the amount of oxygen of the positive electrode active material is a certain value or more, good battery characteristics can be obtained.
又，發現於正極活性物質的粉末X射線繞射(XRD)中，(003)面之繞射波峰之2 θ的半值寬度，與電池特性之間具有密切的相關關係。即，發現當正極活性物質的(003)面之繞射波峰之2 θ的半值寬度在某數值以下時，可得到特別良好的電池特性。 Further, in the powder X-ray diffraction (XRD) of the positive electrode active material, the half value width of 2 θ of the diffraction peak of the (003) plane has a close correlation with the battery characteristics. That is, it was found that when the half value width of 2 θ of the diffraction peak of the (003) plane of the positive electrode active material is a certain value or less, particularly excellent battery characteristics can be obtained.
以上述見解為基礎而完成之本發明，於一態樣中為一種鋰離子電池用正極活性物質，其係以下述組成式表示：Li(LixNi1-x-yMy)O2+α The present invention based on the above findings is, in one aspect, a positive electrode active material for a lithium ion battery, which is represented by the following composition formula: Li(Li x Ni 1-xy M y )O 2+α
(上述式中，0≦x≦0.1，0<y≦0.7，M為金屬，α>0) (In the above formula, 0≦x≦0.1, 0<y≦0.7, M is metal, α>0)
於粉末X射線繞射(XRD)中，(003)面之繞射波峰之2 θ的半值寬度為0.14°以下。 In powder X-ray diffraction (XRD), the half value width of 2 θ of the diffraction peak of the (003) plane is 0.14° or less.
本發明之鋰離子電池用正極活性物質，於一實施形態 中，上述M為選自Sc、Ti、V、Cr、Mn、Fe、Co、Cu、Zn、Ga、Ge、Al、Bi、Sn、Mg、Ca、B及Zr中之1種以上。 The positive electrode active material for a lithium ion battery of the present invention is in one embodiment In the above, M is one or more selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr.
本發明之鋰離子電池用正極活性物質，於另一實施形態中，上述M為選自Mn及Co中之1種以上。 In another embodiment, the M is a positive electrode active material for a lithium ion battery, and the M is one or more selected from the group consisting of Mn and Co.
本發明之鋰離子電池用正極活性物質，於又一實施形態中，上述組成式中，α>0.05。 In still another embodiment of the positive electrode active material for a lithium ion battery of the present invention, in the composition formula, α>0.05.
本發明之鋰離子電池用正極活性物質，於又一實施形態中，上述組成式中，α>0.1。 In still another embodiment of the positive electrode active material for a lithium ion battery of the present invention, in the composition formula, α>0.1.
本發明之鋰離子電池用正極活性物質，於又一實施形態中，於粉末X射線繞射(XRD)中，(104)面與(003)面之繞射波峰強度比〔(104)/(003)〕為0.80以下。 In another embodiment, in the powder X-ray diffraction (XRD), the positive electrode active material for a lithium ion battery of the present invention has a diffraction peak intensity ratio of the (104) plane and the (003) plane [(104)/( 003)] is 0.80 or less.
本發明之鋰離子電池用正極活性物質，於又一實施形態中，於粉末X射線繞射(XRD)中，(110)面之繞射波峰之2 θ為下述式(1)及式(2)表示之2直線所夾持之區域內的數值， In another embodiment, in the powder X-ray diffraction (XRD), the 2θ of the diffraction peak of the (110) plane is expressed by the following formula (1) and formula (1) and (in the embodiment) 2) the value in the area indicated by the 2 straight line,
(1)2 θ=-0.0072c+65.23 (1) 2 θ=-0.0072c+65.23
(2)2 θ=-0.0072c+65.43 (2) 2 θ=-0.0072c+65.43
〔上述式(1)及式(2)中，c為不包括Li之金屬中Ni的莫耳比率〕。 [In the above formulas (1) and (2), c is a molar ratio of Ni in a metal not including Li].
本發明於另一態樣中為一種鋰離子電池用正極，其使用有本發明之鋰離子電池用正極活性物質。 In another aspect, the present invention provides a positive electrode for a lithium ion battery using the positive electrode active material for a lithium ion battery of the present invention.
本發明於再另一態樣中為一種鋰離子電池，其使用有本發明之鋰離子電池用正極。 In still another aspect, the present invention is a lithium ion battery using the positive electrode for a lithium ion battery of the present invention.
根據本發明，可提供一種具有良好電池特性之鋰離子 電池用正極活性物質。 According to the present invention, a lithium ion having good battery characteristics can be provided Positive electrode active material for batteries.
本發明之鋰離子電池用正極活性物質之材料，可廣泛使用適用作為一般鋰離子電池用正極用之正極活性物質的化合物，尤佳使用鈷酸鋰(LiCoO2)、鎳酸鋰(LiNiO2)、錳酸鋰(LiMn2O4)等含鋰之過渡金屬氧化物。使用上述材料而製作之本發明之鋰離子電池用正極活性物質係以下述組成式表示：Li(LixNi1-x-yMy)O2+α The material of the positive electrode active material for a lithium ion battery of the present invention can be widely used as a compound for a positive electrode active material for a positive electrode for a general lithium ion battery, and particularly preferably lithium cobaltate (LiCoO 2 ) or lithium nickelate (LiNiO 2 ). A lithium-containing transition metal oxide such as lithium manganate (LiMn 2 O 4 ). The positive electrode active material for a lithium ion battery of the present invention produced by using the above materials is represented by the following composition formula: Li(Li x Ni 1-xy M y )O 2+α
(上述式中，0≦x≦0.1，0<y≦0.7，M為金屬，α>0)。 (In the above formula, 0≦x≦0.1, 0<y≦0.7, M is a metal, α>0).
又，金屬M亦可選自Sc、Ti、V、Cr、Mn、Fe、Co、Cu、Zn、Ga、Ge、Al、Bi、Sn、Mg、Ca、B及Zr中之1種以上，較佳為選自Mn及Co中之1種以上。 Further, the metal M may be selected from one or more of the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. It is preferably one or more selected from the group consisting of Mn and Co.
本發明之鋰離子電池用正極活性物質之氧，於組成式中如上述，係表示為O2+α(α>0)，過剩地含有，當用於鋰離子電池之情形時，容量、比率特性及容量保持率等電池特性變得良好。此處，關於α，較佳為α>0.05，更佳為α>0.1。 The oxygen of the positive electrode active material for a lithium ion battery of the present invention is expressed as O 2+ α (α>0) as described above in the composition formula, and is excessively contained. When used in a lithium ion battery, the capacity and ratio are used. Battery characteristics such as characteristics and capacity retention rate are good. Here, with respect to α, it is preferably α>0.05, more preferably α>0.1.
本發明之鋰離子電池用正極活性物質，於粉末X射線繞射(XRD)中，(003)面之繞射波峰之2 θ的半值寬度為0.14°以下。藉由如上述般將XRD中之(003)面之繞射波峰之2 θ的半值寬度控制在0.14°以下，正極活性物質的 結晶性變得良好，組成不均變小，因此使用有該正極活性物質之電池的各種特性變好。(003)面之繞射波峰之2 θ的半值寬度較佳為0.135°以下，更佳為0.130°以下，典型為0.110°~0.140°。 In the positive electrode active material for a lithium ion battery of the present invention, in powder X-ray diffraction (XRD), the half value width of 2 θ of the diffraction peak of the (003) plane is 0.14 or less. By controlling the half value width of 2 θ of the diffraction peak of the (003) plane in XRD to 0.14° or less as described above, the positive electrode active material Since the crystallinity is good and the composition unevenness is small, various characteristics of the battery using the positive electrode active material are improved. The half value width of 2 θ of the (003) diffraction peak is preferably 0.135° or less, more preferably 0.130° or less, and typically 0.110° to 0.140°.
本發明之鋰離子電池用正極活性物質，於粉末X射線繞射(XRD)中，(104)面與(003)面之繞射波峰強度比〔(104)/(003)〕在0.80以下為較佳。此繞射波峰強度比係表示Ni之2價離子佔有結晶中之Li位置之(陽離子混合(cation mixing))的基準，若波峰強度比變大，則陽離子混合之比率變多，結晶中之Li位置內之Li的擴散被阻礙，因此使各種電池特性下降。相對於此，若此繞射波峰強度比被控制在0.80以下，則陽離子混合之比率小，結晶中之Li位置內之Li的擴散不會被阻礙，電池特性變得良好。(104)面與(003)面之繞射波峰強度比〔(104)/(003)〕較佳為0.75以下，更佳為0.70以下，典型為0.60~0.80。 In the positive electrode active material for a lithium ion battery of the present invention, in the powder X-ray diffraction (XRD), the diffraction peak intensity ratio ((104)/(003)) of the (104) plane and the (003) plane is 0.80 or less. Preferably. This diffraction peak intensity ratio is a criterion for the cation mixing of Ni in the crystal, and if the peak intensity ratio becomes larger, the ratio of cation mixing becomes larger, and Li in the crystal The diffusion of Li in the position is hindered, so that various battery characteristics are degraded. On the other hand, when the diffraction peak intensity ratio is controlled to 0.80 or less, the ratio of cation mixing is small, and diffusion of Li in the Li position in the crystal is not hindered, and battery characteristics are improved. The diffraction peak intensity ratio ((104) / (003)) of the (104) plane and the (003) plane is preferably 0.75 or less, more preferably 0.70 or less, and typically 0.60 to 0.80.
本發明之鋰離子電池用正極活性物質，於粉末X射線繞射(XRD)中，(110)面之繞射波峰之2 θ較佳為下述式(1)及式(2)表示之2直線所夾持之區域內的數值， In the powder X-ray diffraction (XRD), the positive electrode active material for a lithium ion battery of the present invention preferably has 2 θ of the diffraction peak of the (110) plane as represented by the following formulas (1) and (2). The value in the area held by the line,
(1)2 θ=-0.0072c+65.23 (1) 2 θ=-0.0072c+65.23
(2)2 θ=-0.0072c+65.43 (2) 2 θ=-0.0072c+65.43
〔上述式(1)及式(2)中，c為不包括Li之金屬中Ni的莫耳比率〕。 [In the above formulas (1) and (2), c is a molar ratio of Ni in a metal not including Li].
藉由將(110)面之繞射波峰之2 θ控制成為以式(1) 及式(2)表示之2直線所夾持之區域內的數值，可兼具正極活性物質之氧過剩量組成及良好之結晶性。因此電池的各種特性變得良好。 By controlling 2 θ of the diffraction peak of the (110) plane to be expressed by equation (1) The numerical value in the region sandwiched by the two straight lines represented by the formula (2) can have both the oxygen excess amount composition of the positive electrode active material and good crystallinity. Therefore, various characteristics of the battery become good.
鋰離子電池用正極活性物質係由一次粒子、一次粒子凝聚形成之二次粒子、或一次粒子及二次粒子的混合物構成。鋰離子電池用正極活性物質，較佳為其一次粒子或二次粒子之平均粒徑為2~10μm。 The positive electrode active material for a lithium ion battery is composed of a primary particle, a secondary particle formed by agglomeration of primary particles, or a mixture of primary particles and secondary particles. The positive electrode active material for a lithium ion battery preferably has an average particle diameter of primary particles or secondary particles of 2 to 10 μm.
若平均粒徑未達2μm，則難以塗佈至集電體。若平均粒徑超過10μm，則填充時易產生空隙，使填充性下降。又，平均粒徑更佳為3~9μm。 When the average particle diameter is less than 2 μm, it is difficult to apply to the current collector. When the average particle diameter exceeds 10 μm, voids are likely to occur during filling, and the filling property is lowered. Further, the average particle diameter is more preferably from 3 to 9 μm.
本發明之實施形態的鋰離子電池用正極，例如具有下述構造：將混合上述構成之鋰離子電池用正極活性物質、導電助劑及黏合劑而製備成之正極合劑，設置於由鋁箔等構成之集電體的單面或雙面。又，本發明之實施形態之鋰離子電池，具備有上述構成之鋰離子電池用正極。 The positive electrode for a lithium ion battery according to the embodiment of the present invention has a structure in which a positive electrode mixture prepared by mixing a positive electrode active material for a lithium ion battery, a conductive auxiliary agent, and a binder having the above-described configuration is provided, and is provided in an aluminum foil or the like. One or both sides of the collector. Moreover, the lithium ion battery according to the embodiment of the present invention includes the positive electrode for a lithium ion battery having the above configuration.
其次，詳細說明本發明之實施形態之鋰離子電池用正極活性物質的製造方法。 Next, a method for producing a positive electrode active material for a lithium ion battery according to an embodiment of the present invention will be described in detail.
首先，製作金屬鹽溶液。該金屬為Ni，及選自Sc、Ti、V、Cr、Mn、Fe、Co、Cu、Zn、Ga、Ge、Al、Bi、Sn、Mg、Ca、B及Zr中之1種以上。又，金屬鹽為硫酸鹽、氯化物、硝酸鹽、乙酸鹽等，尤佳為硝酸鹽。其原因在於：即便是以雜質的形態混入燒成原料中，亦可直接燒成，故可省去 清洗步驟；以及硝酸鹽會作為氧化劑而發揮功能，具有促進燒成原料中之金屬之氧化的作用。預先調整金屬鹽中所含各金屬成為所欲莫耳比率。藉此，決定正極活性物質中之各金屬的莫耳比率。 First, a metal salt solution is prepared. The metal is Ni and one or more selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. Further, the metal salt is a sulfate, a chloride, a nitrate, an acetate or the like, and particularly preferably a nitrate. The reason is that even if it is mixed into the calcined raw material in the form of impurities, it can be directly fired, so that it can be omitted. The washing step; and the nitrate function as an oxidizing agent, and has an effect of promoting oxidation of the metal in the firing raw material. The metal contained in the metal salt is adjusted in advance to have a desired molar ratio. Thereby, the molar ratio of each metal in the positive electrode active material is determined.
其次，使碳酸鋰懸浮於純水，其後投入上述金屬之金屬鹽溶液而製作金屬碳酸鹽漿料。此時，漿料中會析出微小粒之含鋰碳酸鹽。再者，於作為金屬鹽之硫酸鹽或氯化物等之熱處理時其鋰化合物不進行反應之情形時，利用飽和碳酸鋰溶液清洗後進行過濾分離。如硝酸鹽或乙酸鹽，其鋰化合物於熱處理過程中作為鋰原料進行反應之情形時，可不進行清洗，而直接過濾分離並加以乾燥，藉此作為燒成前驅物使用。 Next, lithium carbonate was suspended in pure water, and then a metal salt solution of the above metal was introduced to prepare a metal carbonate slurry. At this time, lithium carbonate containing fine particles is precipitated in the slurry. In the case where the lithium compound is not reacted during heat treatment such as a sulfate or a chloride of a metal salt, it is washed with a saturated lithium carbonate solution and then subjected to filtration separation. For example, in the case of a nitrate or acetate, when a lithium compound is reacted as a lithium raw material during heat treatment, it may be used as a firing precursor without being washed, but directly separated by filtration and dried.
其次，藉由將經過濾分離之含鋰碳酸鹽加以乾燥，而獲得鋰鹽之複合體(鋰離子電池正極材料用前驅物)之粉末。 Next, a powder of a lithium salt composite (precursor for a lithium ion battery positive electrode material) is obtained by drying the filtered lithium-containing carbonate.
其次，準備具有特定大小之容量的燒成容器，將鋰離子電池正極材料用前驅物之粉末填充於該燒成容器。其次，將填充有鋰離子電池正極材料用前驅物之粉末的燒成容器移至燒成爐，進行燒成。燒成係藉由在氧氣環境下加熱保持特定時間來進行。又，若於101~202KPa之加壓下進行燒成，則由於會進一步增加組成中之氧量，故較佳。 Next, a firing vessel having a capacity of a specific size is prepared, and a lithium ion battery positive electrode material is filled in the firing vessel with the powder of the precursor. Next, the firing container filled with the powder of the precursor for the positive electrode material for a lithium ion battery is transferred to a baking furnace and fired. The firing is carried out by heating in an oxygen atmosphere for a specific period of time. Further, if the firing is carried out under a pressure of 101 to 202 KPa, the amount of oxygen in the composition is further increased, which is preferable.
本發明之鋰離子電池用正極活性物質藉由控制根據含Ni比率而成之燒成圖案(燒成溫度及其後之降溫的圖案)，可確保含氧量過剩之組成，並於粉末X射線繞射(XRD) 中，使(003)面之繞射波峰之2 θ的半值寬度為0.14°以下，可得到優異之結晶性。具體而言，於上述燒成步驟中，含Ni比率愈高則以愈高的溫度進行燒成。例如，含Ni比率為33.3莫耳%時以750~800℃進行燒成，同樣地，於80莫耳%時則以950~1050℃進行燒成。以上述燒成溫度(保持溫度)保持一定時間後，使溫度下降，惟必須適當地進行此時之降溫步驟。具體而言，自保持溫度至300℃之時間以3~10小時之範圍來進行。於此降溫時間過長，或保持溫度過高之情形時，變得難以保持氧，構成氧化物之氧於組成式之α中會未達0.05。另一方面，於此降溫時間短，或保持溫度過低之情形時，雖然表示氧過剩之組成式的α會為0.05以上，但(003)面之繞射波峰的半值寬度會超過0.14°，結晶性或相均質性變得不足。又，於上述降溫時間較長之情形時，Ni進入Li位置之陽離子混合變得更加顯著。其結果，無論於哪一種情形，比率特性或容量保持率等之結晶性或相均質性相關之電池特性均會變差。 The positive electrode active material for a lithium ion battery of the present invention can ensure a composition having an excessive oxygen content by controlling a firing pattern (a pattern of firing temperature and a cooling pattern) based on a ratio of Ni. Diffraction (XRD) In the middle, the half value width of 2 θ of the diffraction peak of the (003) plane is 0.14° or less, and excellent crystallinity can be obtained. Specifically, in the above-described baking step, the higher the Ni-containing ratio, the higher the temperature is. For example, when the Ni-containing ratio is 33.3 mol%, the firing is performed at 750 to 800 ° C, and similarly, at 80 mol%, the firing is performed at 950 to 1050 ° C. After the baking temperature (holding temperature) is maintained for a predetermined period of time, the temperature is lowered, but the temperature lowering step at this time must be appropriately performed. Specifically, the time from the holding temperature to 300 ° C is carried out in the range of 3 to 10 hours. When the cooling time is too long, or when the temperature is too high, it becomes difficult to maintain oxygen, and the oxygen constituting the oxide may be less than 0.05 in the compositional α. On the other hand, when the cooling time is short or the temperature is kept too low, although the α representing the composition formula of oxygen excess is 0.05 or more, the half value width of the diffraction peak of the (003) plane may exceed 0.14°. Crystallinity or phase homogeneity becomes insufficient. Further, in the case where the above-described cooling time is long, the cation mixing in which Ni enters the Li position becomes more remarkable. As a result, in any case, the battery characteristics related to the crystallinity or the phase homogeneity such as the ratio characteristics or the capacity retention ratio are deteriorated.
以下，提供用以更好地理解本發明及其優點之實施例，但本發明並不限定於此等實施例。 The following examples are provided to better understand the present invention and its advantages, but the invention is not limited to the embodiments.
首先，使表1中記載之投入量的碳酸鋰懸浮於純水3.2公升後，投入4.8公升金屬鹽溶液。此處，金屬鹽溶液係調整各金屬之硝酸鹽的水合物，使各金屬成為表1中記載之組成比，又，調整成使全部金屬莫耳數為14莫耳。 First, the amount of lithium carbonate described in Table 1 was suspended in 3.2 liters of pure water, and then 4.8 liters of the metal salt solution was charged. Here, the metal salt solution adjusts the hydrate of the nitrate of each metal, and each metal has the composition ratio shown in Table 1, and is adjusted so that the total metal mole number is 14 mol.
再者，碳酸鋰之懸浮量為以Li(LixNi1-x-yMy)O2+α表示製品(鋰離子二次電池正極材料，即正極活性物質)且x為表1之值的量，分別由下式算出者。 Further, the amount of lithium carbonate suspended is a product represented by Li(Li x Ni 1-xy M y )O 2+α (a positive electrode material of a lithium ion secondary battery, that is, a positive electrode active material) and x is a value of Table 1. , which are calculated by the following formulas.
W(g)=73.9×14×(1+0.5{(1+X)/(1-X)})×A W(g)=73.9×14×(1+0.5{(1+X)/(1-X)})×A
上述式中，「A」係用以除了作為析出反應必需之量外，預先自懸浮量減去過濾後原料中殘留之碳酸鋰以外的鋰化合物之鋰量而乘的數值。「A」，如硝酸鹽或乙酸鹽於鋰鹽作為燒成原料進行反應之情形時為0.9，如硫酸鹽或氯化物於鋰鹽未作為燒成原料進行反應之情形時為1.0。 In the above formula, "A" is a value obtained by multiplying the amount of lithium of the lithium compound other than the lithium carbonate remaining in the filtered raw material from the amount of suspension in addition to the amount necessary for the precipitation reaction. "A" is 0.9 when the nitrate or acetate is reacted as a raw material of the lithium salt, and is 1.0 when the sulfate or chloride is not reacted as a raw material for the calcination.
藉由該處理，於溶液中會析出微小粒之含鋰碳酸鹽，使用壓濾機將該析出物過濾分離。 By this treatment, lithium carbonate containing fine particles was precipitated in the solution, and the precipitate was separated by filtration using a filter press.
繼而，將析出物加以乾燥而獲得含鋰碳酸鹽(鋰離子電池正極材料用前驅物)。 Then, the precipitate was dried to obtain a lithium-containing carbonate (precursor for a positive electrode material for a lithium ion battery).
其次，準備燒成容器，將含鋰碳酸鹽填充於該燒成容器內。其次，將燒成容器於大氣壓下放入氧氣環境爐，以表1中記載之燒成溫度加熱保持10小時後，以表1中記載之時間冷卻至300℃。其次，冷卻至室溫後，進行粉碎，而獲得鋰離子二次電池正極材料之粉末。 Next, a baking container is prepared, and a lithium-containing carbonate is filled in the baking container. Next, the baking container was placed in an oxygen atmosphere furnace under atmospheric pressure, and heated and held at the baking temperature shown in Table 1 for 10 hours, and then cooled to 300 ° C in the time shown in Table 1. Next, after cooling to room temperature, pulverization was carried out to obtain a powder of a positive electrode material of a lithium ion secondary battery.
實施例14，係使原料之各金屬為表1所示組成，使金屬鹽為氯化物，析出含鋰碳酸鹽後，利用飽和碳酸鋰溶液進行清洗、過濾，除此之外，皆進行與實施例1~13相同之處理。 In the fourteenth embodiment, each metal of the raw material is a composition shown in Table 1, and the metal salt is a chloride. The lithium-containing carbonate is precipitated, and then washed and filtered with a saturated lithium carbonate solution, and all of them are carried out and carried out. The same processing as in Examples 1 to 13.
實施例15，係使原料之各金屬為表1所示組成，使金屬鹽為硫酸鹽，析出含鋰碳酸鹽後，利用飽和碳酸鋰溶液進行清洗、過濾，除此之外，皆進行與實施例1~13相同之處理。 In the fifteenth embodiment, each metal of the raw material is a composition shown in Table 1, and the metal salt is a sulfate. After the lithium carbonate is precipitated, it is washed and filtered with a saturated lithium carbonate solution, and all of them are carried out and carried out. The same processing as in Examples 1 to 13.
實施例16，係使原料之各金屬為表1所示組成，並非於大氣壓下而是於120KPa之加壓下進行燒成，除此之外，皆進行與實施例1~13相同之處理。 In the same manner as in Examples 1 to 13, the same treatment as in Examples 1 to 13 was carried out except that the respective metals of the raw materials were the compositions shown in Table 1 and were not calcined under atmospheric pressure but under a pressure of 120 KPa.
比較例1~11，係使原料之各金屬為表1所示組成，燒成步驟之保持溫度及降溫時間為表1所示之值，並進行與實施例1~13相同之處理。 In Comparative Examples 1 to 11, the respective metals of the raw materials were the compositions shown in Table 1, and the holding temperature and the cooling time of the baking step were the values shown in Table 1, and the same treatments as in Examples 1 to 13 were carried out.
各正極材料中之金屬含量係利用感應耦合電漿發射光譜分析儀(ICP-OES)測量，而算出各金屬之組成比(莫耳比)。確認各金屬之組成比如表1記載所示。又，含氧量係利用LECO法測量並算出α。 The metal content in each of the positive electrode materials was measured by an inductively coupled plasma emission spectrometer (ICP-OES) to calculate the composition ratio (mol ratio) of each metal. The composition of each metal was confirmed as shown in Table 1. Further, the oxygen content was measured by the LECO method and α was calculated.
藉由粉末X射線繞射(XRD)分別測定(003)面之繞射波峰之2 θ的半值寬度、(110)面之繞射波峰之2 θ、(104)面與(003)面之繞射波峰強度比〔(104)/(003)〕。 The half-value width of 2 θ of the diffraction peak of the (003) plane, the 2 θ of the diffraction peak of the (110) plane, the (104) plane and the (003) plane are respectively determined by powder X-ray diffraction (XRD). The diffraction peak intensity ratio [(104) / (003)].
以85：8：7之比例秤量各正極材料、導電材料與黏合 劑，將黏合劑溶解於有機溶劑(N-甲基吡咯啶酮(N-methylpyrrolidone))後，再將正極材料與導電材料混合於其中進行漿料化，塗佈於Al箔上加以乾燥後進行壓製而製成正極。繼而，製作相對電極為Li之評價用2032型硬幣電池(coin cell)，使用1M-LiPF6溶解於EC-DMC(1：1)而成者作為電解液，測量電流密度0.2C時之放電容量。又，算出電流密度2C時相對於電流密度0.2C時之電池容量的放電容量之比，獲得比率特性。並且，容量保持率，係藉由在室溫下將1C之放電電流所獲得之初始放電容量與100循環後之放電容量加以比較而測得。 The positive electrode material, the conductive material and the binder are weighed in a ratio of 85:8:7, and the binder is dissolved in an organic solvent (N-methylpyrrolidone), and then the positive electrode material is mixed with the conductive material. The slurry was applied thereto, coated on an Al foil, dried, and pressed to prepare a positive electrode. Then, a 2032 coin cell for evaluation of Li as a counter electrode was prepared, and 1 M-LiPF 6 was dissolved in EC-DMC (1:1) as an electrolyte solution, and a discharge capacity at a current density of 0.2 C was measured. . Moreover, the ratio of the discharge capacity of the battery capacity with respect to the current density of 0.2 C at the current density 2C was calculated, and the ratio characteristic was obtained. Further, the capacity retention ratio was measured by comparing the initial discharge capacity obtained by discharging a current of 1 C at room temperature with the discharge capacity after 100 cycles.
該等之結果示於表1及2。 The results of these are shown in Tables 1 and 2.
實施例1~13其電池特性皆為良好。 The battery characteristics of Examples 1 to 13 were all good.
雖然實施例14、15其電池特性皆良好，但並非如實施例1~13般使用各金屬之硝酸鹽的水合物作為原料，而是使用氯化物或硫酸鹽之水合物作為原料，因此電池特性比實施例1~13差。 Although the battery characteristics of Examples 14 and 15 were all good, the hydrate of each metal nitrate was not used as a raw material as in Examples 1 to 13, but a chloride or sulfate hydrate was used as a raw material, so that battery characteristics were obtained. It is inferior to Examples 1 to 13.
實施例16係如實施例1~13般使用各金屬之硝酸鹽的 水合物作為原料，且進一步於加壓下進行燒成，電池特性為最好。 Example 16 uses the nitrate of each metal as in Examples 1-13. The hydrate is used as a raw material, and further baked under pressure, and battery characteristics are the best.
比較例1~4係因為於燒成步驟中至300℃之降溫時間短，因此電池特性不良。 In Comparative Examples 1 to 4, since the cooling time to 300 ° C in the firing step was short, the battery characteristics were poor.
比較例5~8係因為其組成中無法確保氧過剩之組成，因此電池特性不良。 In Comparative Examples 5 to 8, the battery characteristics were poor because the composition of oxygen excess could not be ensured in the composition.
比較例9~11其燒成溫度低，電池特性不良。 In Comparative Examples 9 to 11, the firing temperature was low and the battery characteristics were poor.
又，針對上述實施例及比較例，將不包括Li之金屬中Ni的莫耳比率：c與(110)面之繞射波峰之2 θ設為x軸及y軸，從而描繪了圖1之圖表。根據圖1，實施例全部皆在下述式(1)及式(2)表示之2直線所夾持的區域內，比較例除了一部分以外，全落於此區域之外。 Further, in the above-described examples and comparative examples, the molar ratio of Ni in the metal excluding Li and the 2 θ of the diffraction peak of the (110) plane were set to the x-axis and the y-axis, thereby depicting FIG. chart. According to Fig. 1, all of the examples are in the region sandwiched by the two straight lines represented by the following formulas (1) and (2), and the comparative examples are all outside the region except for a part.
(1)2 θ=-0.0072c+65.23 (1) 2 θ=-0.0072c+65.23
(2)2 θ=-0.0072c+65.43 (2) 2 θ=-0.0072c+65.43
圖1係表示實施例及比較例之不包括Li之金屬中Ni的莫耳比率：c與(110)面之繞射波峰之2 θ的關係之圖表。 Fig. 1 is a graph showing the relationship between the molar ratio of Ni in the metal of Li and the metal of the comparative example and the comparative example, and the relationship between c and the diffraction peak of the (110) plane.
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