JPWO2012073551A1 - Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery - Google Patents
Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery Download PDFInfo
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- 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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- H01M4/505—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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Abstract
リチウムイオン電池用正極活物質は、組成式：Ｌｉ（ＬｉxＮｉ1-x-yＭy）Ｏ2+α（前記式において、Ｍは必須成分としてのＣｏ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｌ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上であり、０≦ｘ≦０．１であり、０＜ｙ≦０．７であり、α＞０である。）で表され、粒度分布のメディアン径が１〜２０μｍであって、安息角が８０°以下である。Cathode active material for lithium ion batteries, the composition formula: in Li (Li x Ni 1-xy M y) O 2 + α ( the equation, M is Co as essential components, and, Sc, Ti, V, Cr, One or more selected from Mn, Fe, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr, 0 ≦ x ≦ 0.1, and 0 <y ≦ 0 7 and α> 0), the median diameter of the particle size distribution is 1 to 20 μm, and the angle of repose is 80 ° or less.
Description
本発明は、リチウムイオン電池用正極活物質、リチウムイオン電池用正極、及び、リチウムイオン電池に関する。 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.
リチウムイオン電池の正極活物質には、一般にリチウム含有遷移金属酸化物が用いられている。具体的には、コバルト酸リチウム（ＬｉＣｏＯ2）、ニッケル酸リチウム（ＬｉＮｉＯ2）、マンガン酸リチウム（ＬｉＭｎ2Ｏ4）等であり、特性改善（高容量化、サイクル特性、保存特性、内部抵抗低減、レート特性）や安全性を高めるためにこれらを複合化することが進められている。車載用やロードレベリング用といった大型用途におけるリチウムイオン電池には、これまでの携帯電話用やパソコン用とは異なった特性が求められている。Lithium-containing transition metal oxides are generally used as positive electrode active materials for lithium ion batteries. Specifically, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), etc., improved characteristics (higher capacity, cycle characteristics, storage characteristics, reduced internal resistance) In order to improve the rate characteristics and safety, it is underway to combine them. Lithium ion batteries for large-scale applications such as in-vehicle use and load leveling are required to have different characteristics from those of conventional mobile phones and personal computers.
電池特性の改善には、従来、種々の方法が用いられており、例えば特許文献１には、
ＬｉxＮｉ1-yＭyＯ2-δ
（０．８≦ｘ≦１．３、０＜ｙ≦０．５であり、Ｍは、Ｃｏ、Ｍｎ、Ｆｅ、Ｃｒ、Ｖ、Ｔｉ、Ｃｕ、Ａｌ、Ｇａ、Ｂｉ、Ｓｎ、Ｚｎ、Ｍｇ、Ｇｅ、Ｎｂ、Ｔａ、Ｂｅ、Ｂ、Ｃａ、Ｓｃ及びＺｒからなる群から選ばれる少なくとも一種の元素を示し、δは酸素欠損又は酸素過剰量に相当し、−０．１＜δ＜０．１を表す。）の組成で表されるリチウムニッケル複合酸化物を分級機に通し、粒子径の大きい物と小さい物とに平衡分離粒子径Ｄｈ＝１〜１０μｍで分離し、粒子径の大きい物と小さい物を、重量比で０：１００〜１００：０で配合することを特徴とするリチウム二次電池用正極材料の製造方法が開示されている。そして、これによれば、レート特性と容量のさまざまなバランスのリチウム二次電池用正極材料を容易に製造できる、と記載されている。Various methods have been conventionally used to improve battery characteristics. For example, Patent Document 1 discloses:
Li x Ni 1- y My O 2- δ
(0.8 ≦ x ≦ 1.3, 0 <y ≦ 0.5, and M is Co, Mn, Fe, Cr, V, Ti, Cu, Al, Ga, Bi, Sn, Zn, Mg, It represents at least one element selected from the group consisting of Ge, Nb, Ta, Be, B, Ca, Sc and Zr, δ corresponds to oxygen deficiency or oxygen excess, and −0.1 <δ <0.1 The lithium nickel composite oxide represented by the composition is passed through a classifier and separated into a large particle size and a small particle size with an equilibrium separation particle size Dh = 1 to 10 μm, and a large particle size A method for producing a positive electrode material for a lithium secondary battery, characterized in that small substances are blended at a weight ratio of 0: 100 to 100: 0. And according to this, it is described that the positive electrode material for lithium secondary batteries with various balance of rate characteristics and capacity can be easily manufactured.
特許文献１に記載のリチウムニッケル複合酸化物は、その組成式中の酸素量が過剰のものであるが、それでもなお高品質のリチウムイオン電池用正極活物質としては改善の余地がある。 Although the lithium nickel composite oxide described in Patent Document 1 has an excessive amount of oxygen in its composition formula, there is still room for improvement as a high-quality positive electrode active material for a lithium ion battery.
そこで、本発明は、良好な電池特性を有するリチウムイオン電池用正極活物質を提供することを課題とする。 Then, this invention makes it a subject to provide the positive electrode active material for lithium ion batteries which has a favorable battery characteristic.
本発明者らは、鋭意検討した結果、正極活物質の酸素量と電池特性との間に密接な相関関係があることを見出した。すなわち、正極活物質の酸素量がある値以上であるとき、特に良好な電池特性が得られることを見出した。また、酸素量がある値以上である正極活物質において、粉体の粒度分布及び安息角を制御することにより、より良好な電池特性が得られることを見出した。 As a result of intensive studies, the present inventors have 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 has been found that particularly good battery characteristics can be obtained when the amount of oxygen in the positive electrode active material is greater than or equal to a certain value. Further, it has been found that better battery characteristics can be obtained by controlling the particle size distribution and angle of repose of the powder in a positive electrode active material having an oxygen amount of a certain value or more.
上記知見を基礎にして完成した本発明は一側面において、
組成式：Ｌｉ（ＬｉxＮｉ1-x-yＭy）Ｏ2+α
（前記式において、Ｍは必須成分としてのＣｏ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｌ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上であり、０≦ｘ≦０．１であり、０＜ｙ≦０．７であり、α＞０である。）
で表され、
粒度分布のメディアン径が１〜２０μｍであって、安息角が８０°以下であるリチウムイオン電池用正極活物質である。In one aspect of the present invention completed based on the above knowledge,
Composition formula: Li (Li x Ni 1- xy M y) O 2 + α
(In the above formula, M is selected from Co as an essential component and Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. 1 or more selected from the above, 0 ≦ x ≦ 0.1, 0 <y ≦ 0.7, and α> 0.)
Represented by
It is a positive electrode active material for a lithium ion battery having a median diameter of 1 to 20 μm and a repose angle of 80 ° or less.
本発明に係るリチウムイオン電池用正極活物質は一実施形態において、安息角が３０〜８０°である。 In one embodiment, the positive electrode active material for a lithium ion battery according to the present invention has an angle of repose of 30 to 80 °.
本発明に係るリチウムイオン電池用正極活物質は別の実施形態において、安息角が５０〜８０°である。 In another embodiment, the positive electrode active material for a lithium ion battery according to the present invention has an angle of repose of 50 to 80 °.
本発明に係るリチウムイオン電池用正極活物質は更に別の実施形態において、メディアン径が５〜１７μｍである。 In still another embodiment, the positive electrode active material for a lithium ion battery according to the present invention has a median diameter of 5 to 17 μm.
本発明に係るリチウムイオン電池用正極活物質は別の実施形態において、Ｍが、Ｍｎ及びＣｏから選択される１種以上である。 In another embodiment of the positive electrode active material for a lithium ion battery according to the present invention, M is at least one selected from Mn and Co.
本発明に係るリチウムイオン電池用正極活物質は更に別の実施形態において、組成式において、α＞０．０５である。 In still another embodiment, the positive electrode active material for a lithium ion battery according to the present invention has α> 0.05 in the composition formula.
本発明に係るリチウムイオン電池用正極活物質は更に別の実施形態において、組成式において、α＞０．１である。 In still another embodiment, the positive electrode active material for a lithium ion battery according to the present invention has α> 0.1 in the composition formula.
本発明に係るリチウムイオン電池用正極活物質は更に別の実施形態において、比表面積が０．２〜１．０ｃｍ2／ｇである。In yet another embodiment, the positive electrode active material for a lithium ion battery according to the present invention has a specific surface area of 0.2 to 1.0 cm 2 / g.
本発明に係るリチウムイオン電池用正極活物質は更に別の実施形態において、比表面積が０．３〜０．７ｃｍ2／ｇである。In yet another embodiment, the positive electrode active material for a lithium ion battery according to the present invention has a specific surface area of 0.3 to 0.7 cm 2 / g.
本発明は、別の側面において、本発明に係るリチウムイオン電池用正極活物質を用いたリチウムイオン電池用正極である。 In another aspect, the present invention is a positive electrode for a lithium ion battery using the positive electrode active material for a lithium ion battery according to the present invention.
本発明は、更に別の側面において、本発明に係るリチウムイオン電池用正極を用いたリチウムイオン電池である。 In still another aspect, the present invention is a lithium ion battery using the positive electrode for a lithium ion battery according to the present invention.
本発明によれば、良好な電池特性を有するリチウムイオン電池用正極活物質を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the positive electrode active material for lithium ion batteries which has a favorable battery characteristic can be provided.
（リチウムイオン電池用正極活物質の構成）
本発明のリチウムイオン電池用正極活物質の材料としては、一般的なリチウムイオン電池用正極用の正極活物質として有用な化合物を広く用いることができるが、特に、コバルト酸リチウム（ＬｉＣｏＯ2）、ニッケル酸リチウム（ＬｉＮｉＯ2）、マンガン酸リチウム（ＬｉＭｎ2Ｏ4）等のリチウム含有遷移金属酸化物を用いるのが好ましい。このような材料を用いて作製される本発明のリチウムイオン電池用正極活物質は、
組成式：Ｌｉ（ＬｉxＮｉ1-x-yＭy）Ｏ2+α
（前記式において、Ｍは必須成分としてのＣｏ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｌ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上であり、０≦ｘ≦０．１であり、０＜ｙ≦０．７であり、α＞０である。）
で表される。(Configuration of positive electrode active material for lithium ion battery)
As a material of the positive electrode active material for lithium ion batteries of the present invention, compounds useful as a positive electrode active material for general positive electrodes for lithium ion batteries can be widely used. In particular, lithium cobaltate (LiCoO 2 ), It is preferable to use lithium-containing transition metal oxides such as lithium nickelate (LiNiO 2 ) and lithium manganate (LiMn 2 O 4 ). The positive electrode active material for a lithium ion battery of the present invention produced using such a material is
Composition formula: Li (Li x Ni 1- xy M y) O 2 + α
(In the above formula, M is selected from Co as an essential component and Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. 1 or more selected from the above, 0 ≦ x ≦ 0.1, 0 <y ≦ 0.7, and α> 0.)
It is represented by
本発明のリチウムイオン電池用正極活物質は、酸素が組成式において上記のようにＯ2+α（α＞０）と示され、過剰に含まれており、リチウムイオン電池に用いた場合、容量、レート特性及び容量保持率等の電池特性が良好となる。ここで、αについて、好ましくはα＞０．０５であり、より好ましくはα＞０．１である。The positive electrode active material for a lithium ion battery according to the present invention has oxygen as O 2 + α (α> 0) as described above in the composition formula, and is contained excessively. Battery characteristics such as rate characteristics and capacity retention are improved. Here, α is preferably α> 0.05, and more preferably α> 0.1.
本発明のリチウムイオン電池用正極活物質は、一次粒子、一次粒子が凝集して形成された二次粒子、又は、一次粒子及び二次粒子の混合物で構成されている。これらの一次粒子、一次粒子が凝集して形成された二次粒子、又は、一次粒子及び二次粒子の混合物の粒度分布のメディアン径（平均粒径の中央値）は１〜２０μｍである。メディアン径が１〜２０μｍであれば、ばらつきが抑制された粉体となり、リチウムイオン電池の電極作製時の活物質の均一な塗布が可能となり、さらに電極組成のばらつきを抑制することができる。このため、リチウムイオン電池に用いたときに、レート特性及びサイクル特性が良好となる。メディアン径は、好ましくは５〜１７μｍである。 The positive electrode active material for a lithium ion battery of the present invention is composed of primary particles, secondary particles formed by aggregation of primary particles, or a mixture of primary particles and secondary particles. The median diameter (median value of the average particle diameter) of the particle size distribution of these primary particles, secondary particles formed by aggregation of the primary particles, or a mixture of primary particles and secondary particles is 1 to 20 μm. If the median diameter is 1 to 20 μm, the powder is suppressed in variation, the active material can be uniformly applied during the production of the electrode of the lithium ion battery, and variation in the electrode composition can be further suppressed. For this reason, when it uses for a lithium ion battery, a rate characteristic and cycling characteristics become favorable. The median diameter is preferably 5 to 17 μm.
本発明のリチウムイオン電池用正極活物質は、安息角が８０°以下である。ここで、安息角とは、粉体を上方から静かに落下させて生じる円錐状堆積層が、水平面との間に作る傾斜角である。安息角は粉体粒子間の付着力を表す指標であり、この安息角の値が小さい粉体粒子ほど、凝集性が弱く流動性がよい、即ち、まとわりつきにくい性質を有しているといえる。安息角を８０°以下とすることで、ばらつきを抑制してリチウムイオン電池の電極作製時の活物質の均一な塗布を可能とし、さらに電極組成のばらつきを抑制することができる。従って、リチウムイオン電池に用いたときに、レート特性及びサイクル特性が良好となる。ただし、凝集性が弱すぎると、分散されやすいが、電極のスラリーを製造する際各粒子がバインダーによって失活されやすくなる。このため、適度なまとわりつきやすさが必要となる。このような観点から、安息角は、典型的には１５〜８０°であり、好ましくは３０〜８０°、より好ましくは５０〜８０°である。 The positive electrode active material for lithium ion batteries of the present invention has an angle of repose of 80 ° or less. Here, the angle of repose is an angle of inclination formed between a horizontal plane and a conical sedimentary layer generated by gently dropping powder from above. The angle of repose is an index representing the adhesive force between the powder particles, and the smaller the angle of repose angle, the weaker the cohesiveness and the better the fluidity, that is, it can be said that the repose angle has a property that is difficult to cling. By setting the angle of repose to 80 ° or less, it is possible to suppress variation and enable uniform application of the active material during the production of an electrode of a lithium ion battery, and further suppress variation in electrode composition. Therefore, when used in a lithium ion battery, rate characteristics and cycle characteristics are improved. However, if the cohesiveness is too weak, the particles are easily dispersed, but each particle is easily deactivated by the binder when the slurry of the electrode is produced. For this reason, a moderate ease of attachment is required. From such a viewpoint, the angle of repose is typically 15 to 80 °, preferably 30 to 80 °, and more preferably 50 to 80 °.
本発明のリチウムイオン電池用正極活物質は、比表面積が０．２〜１．０ｃｍ2／ｇである。比表面積が０．２〜１．０ｃｍ2／ｇであれば、電解液との反応が抑制されサイクル特性が改善される。比表面積は、好ましくは０．３〜０．７ｃｍ2／ｇである。The positive electrode active material for a lithium ion battery of the present invention has a specific surface area of 0.2 to 1.0 cm 2 / g. When the specific surface area is 0.2 to 1.0 cm 2 / g, reaction with the electrolytic solution is suppressed and cycle characteristics are improved. The specific surface area is preferably 0.3 to 0.7 cm 2 / g.
（リチウムイオン電池用正極及びそれを用いたリチウムイオン電池の構成）
本発明の実施形態に係るリチウムイオン電池用正極は、例えば、上述の構成のリチウムイオン電池用正極活物質と、導電助剤と、バインダーとを混合して調製した正極合剤をアルミニウム箔等からなる集電体の片面または両面に設けた構造を有している。また、本発明の実施形態に係るリチウムイオン電池は、このような構成のリチウムイオン電池用正極を備えている。(Configuration of positive electrode for lithium ion battery and lithium ion battery using the same)
The positive electrode for a lithium ion battery according to an embodiment of the present invention includes, for example, a positive electrode mixture prepared by mixing a positive electrode active material for a lithium ion battery having the above-described configuration, a conductive additive, and a binder from an aluminum foil or the like. The current collector has a structure provided on one side or both sides. Moreover, the lithium ion battery which concerns on embodiment of this invention is equipped with the positive electrode for lithium ion batteries of such a structure.
（リチウムイオン電池用正極活物質の製造方法）
次に、本発明の実施形態に係るリチウムイオン電池用正極活物質の製造方法について詳細に説明する。
まず、金属塩溶液を作製する。当該金属は、Ｎｉ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｌ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上である。また、金属塩は硫酸塩、塩化物、硝酸塩、酢酸塩等であり、特に硝酸塩が好ましい。これは、焼成原料中に不純物として混入してもそのまま焼成できるため洗浄工程が省けることと、硝酸塩が酸化剤として機能し、焼成原料中の金属の酸化を促進する働きがあるためである。金属塩に含まれる各金属を所望のモル比率となるように調整しておく。これにより、正極活物質中の各金属のモル比率が決定する。(Method for producing positive electrode active material for lithium ion battery)
Next, the manufacturing method of the positive electrode active material for lithium ion batteries which concerns on embodiment of this invention is demonstrated in detail.
First, a metal salt solution is prepared. The metal is at least one selected from Ni and Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. It is. The metal salt is sulfate, chloride, nitrate, acetate, etc., and nitrate is particularly preferable. This is because even if it is mixed as an impurity in the firing raw material, it can be fired as it is, so that the washing step can be omitted, and nitrate functions as an oxidant, and promotes the oxidation of the metal in the firing raw material. Each metal contained in the metal salt is adjusted so as to have a desired molar ratio. Thereby, the molar ratio of each metal in the positive electrode active material is determined.
次に、炭酸リチウムを純水に懸濁させ、その後、上記金属の金属塩溶液を投入して金属炭酸塩溶液スラリーを作製する。このとき、スラリー中に微小粒のリチウム含有炭酸塩が析出する。なお、金属塩として硫酸塩や塩化物等熱処理時にそのリチウム化合物が反応しない場合は飽和炭酸リチウム溶液で洗浄した後、濾別する。硝酸塩や酢酸塩のように、そのリチウム化合物が熱処理中にリチウム原料として反応する場合は洗浄せず、そのまま濾別し、乾燥することにより焼成前駆体として用いることができる。
次に、濾別したリチウム含有炭酸塩を乾燥することにより、リチウム塩の複合体（リチウムイオン電池正極材用前駆体）の粉末を得る。Next, lithium carbonate is suspended in pure water, and then the metal salt solution of the metal is added to prepare a metal carbonate solution slurry. At this time, fine particles of lithium-containing carbonate precipitate in the slurry. If the lithium compound does not react during heat treatment such as sulfate or chloride as a metal salt, it is washed with a saturated lithium carbonate solution and then filtered off. When the lithium compound reacts as a lithium raw material during the heat treatment, such as nitrate or acetate, it can be used as a calcined precursor by washing and drying as it is without washing.
Next, the lithium-containing carbonate separated by filtration is dried to obtain a lithium salt composite (precursor for lithium ion battery positive electrode material) powder.
次に、乾燥して得られたリチウムイオン電池正極材用前駆体の粉末を、篩、又は、市販の分級装置等を用いて分級し、１〜３０μｍの粒径の粉末のみを得る。 Next, the powder of the precursor for a lithium ion battery positive electrode material obtained by drying is classified using a sieve, a commercially available classifier, or the like to obtain only a powder having a particle diameter of 1 to 30 μm.
次に、所定の大きさの容量を有する焼成容器を準備し、この焼成容器に分級した１〜３０μｍの粒径のリチウムイオン電池正極材用前駆体の粉末を充填する。次に、リチウムイオン電池正極材用前駆体の粉末が充填された焼成容器を、焼成炉へ移設し、焼成を行う。焼成は、酸素雰囲気下で所定時間加熱保持することにより行う。また、１０１〜２０２ＫＰａでの加圧下で焼成を行うと、さらに組成中の酸素量が増加するため、好ましい。
その後、焼成容器から粉末を取り出し、市販の粉砕装置等を用いて解砕を行うことにより正極活物質の粉体を得る。このときの解砕は、所望のメディアン径及び安息角が得られるように、適宜粉砕強度及び粉砕時間を調整して行う。Next, a firing container having a capacity of a predetermined size is prepared, and the powder of a precursor for a lithium ion battery positive electrode material having a particle diameter of 1 to 30 μm is filled in the firing container. Next, the firing container filled with the precursor powder for the lithium ion battery positive electrode material is transferred to a firing furnace and fired. Firing is performed by heating and holding in an oxygen atmosphere for a predetermined time. Further, it is preferable to perform baking under pressure of 101 to 202 KPa because the amount of oxygen in the composition further increases.
Thereafter, the powder is taken out from the firing container and pulverized using a commercially available pulverizer or the like to obtain a positive electrode active material powder. The crushing at this time is performed by appropriately adjusting the crushing strength and crushing time so that a desired median diameter and angle of repose can be obtained.
以下、本発明及びその利点をより良く理解するための実施例を提供するが、本発明はこれらの実施例に限られるものではない。 Examples for better understanding of the present invention and its advantages are provided below, but the present invention is not limited to these examples.
（実施例１〜１５）
まず、表１に記載の投入量の炭酸リチウムを純水３．２リットルに懸濁させた後、金属塩溶液を４．８リットル投入した。ここで、金属塩溶液は、各金属の硝酸塩の水和物を、各金属が表１に記載の組成比になるように調整し、また全金属モル数が１４モルになるように調整した。
なお、炭酸リチウムの懸濁量は、製品（リチウムイオン二次電池正極材料、すなわち正極活物質）をＬｉ（ＬｉxＮｉ1-x-yＭy）Ｏ2+αでｘが表１の値となる量であって、それぞれ次式で算出されたものである。
Ｗ（ｇ）＝７３．９×１４×（１＋０．５{（１＋Ｘ）/（１−Ｘ）}×Ａ
上記式において、「Ａ」は、析出反応として必要な量の他に、ろ過後の原料に残留する炭酸リチウム以外のリチウム化合物によるリチウムの量をあらかじめ懸濁量から引いておくために掛ける数値である。「Ａ」は、硝酸塩や酢酸塩のように、リチウム塩が焼成原料として反応する場合は０．９であり、硫酸塩や塩化物のように、リチウム塩が焼成原料として反応しない場合は１．０である。
この処理により溶液中に微小粒のリチウム含有炭酸塩が析出したが、この析出物を、フィルタープレスを使用して濾別した。
続いて、析出物を乾燥してリチウム含有炭酸塩（リチウムイオン電池正極材用前駆体）を得た。
次に、乾燥して得たリチウム含有炭酸塩を篩にかけて、１〜３０μｍの粒径のものに分級した。
次に、焼成容器を準備し、この焼成容器内にリチウム含有炭酸塩を充填した。次に、焼成容器を、大気圧下、酸素雰囲気炉に入れて、表１に記載の焼成温度で１０時間加熱保持した後冷却して酸化物を得た。
次に、得られた酸化物を小型粉砕機（ホソカワミクロンＡＣＭ-2ＥＣ）を用いてメディアン粒径１〜２０μｍに解砕し、リチウムイオン二次電池正極材の粉末を得た。(Examples 1 to 15)
First, after suspending lithium carbonate of the input amount shown in Table 1 in 3.2 liters of pure water, 4.8 liter of metal salt solution was charged. Here, the nitrate hydrate of each metal was adjusted so that each metal might become the composition ratio of Table 1, and the total metal mole number might be set to 14 mol.
Incidentally, a suspension of lithium carbonate, the product (lithium ion secondary battery positive electrode material, i.e. a cathode active material) x with Li (Li x Ni 1-xy M y) O 2 + α becomes a value shown in Table 1 Each of which is calculated by the following equation.
W (g) = 73.9 × 14 × (1 + 0.5 {(1 + X) / (1-X)} × A
In the above formula, “A” is a numerical value to be multiplied in order to subtract the amount of lithium from the lithium compound other than lithium carbonate remaining in the raw material after filtration from the amount of suspension in addition to the amount necessary for the precipitation reaction. is there. “A” is 0.9 when lithium salt reacts as a firing raw material such as nitrate or acetate, and “1” when lithium salt does not react as a firing raw material such as sulfate or chloride. 0.
By this treatment, fine particles of lithium-containing carbonate were precipitated in the solution, and this precipitate was filtered off using a filter press.
Subsequently, the precipitate was dried to obtain a lithium-containing carbonate (a precursor for a lithium ion battery positive electrode material).
Next, the lithium-containing carbonate obtained by drying was sieved and classified into particles having a particle size of 1 to 30 μm.
Next, a firing container was prepared, and this firing container was filled with a lithium-containing carbonate. Next, the firing container was placed in an oxygen atmosphere furnace under atmospheric pressure, heated and held at the firing temperature shown in Table 1 for 10 hours, and then cooled to obtain an oxide.
Next, the obtained oxide was pulverized to a median particle size of 1 to 20 μm using a small pulverizer (Hosokawa Micron ACM-2EC) to obtain a powder of a lithium ion secondary battery positive electrode material.
（実施例１６）
実施例１６として、原料の各金属を表１に示すような組成とし、金属塩を塩化物とし、リチウム含有炭酸塩を析出させた後、飽和炭酸リチウム溶液で洗浄し、濾過する以外は、実施例１〜１５と同様の処理を行った。(Example 16)
Example 16 was carried out except that each raw material had a composition as shown in Table 1, the metal salt was chloride, lithium-containing carbonate was precipitated, washed with a saturated lithium carbonate solution, and filtered. The same treatment as in Examples 1 to 15 was performed.
（実施例１７）
実施例１７として、原料の各金属を表１に示すような組成とし、金属塩を硫酸塩とし、リチウム含有炭酸塩を析出させた後、飽和炭酸リチウム溶液で洗浄し、濾過する以外は、実施例１〜１５と同様の処理を行った。(Example 17)
Example 17 was carried out except that each material of the raw material had the composition shown in Table 1, the metal salt was sulfate, the lithium-containing carbonate was precipitated, washed with a saturated lithium carbonate solution, and filtered. The same treatment as in Examples 1 to 15 was performed.
（実施例１８）
実施例１８として、原料の各金属を表１に示すような組成とし、焼成を大気圧下ではなく１２０ＫＰａの加圧下で行った以外は、実施例１〜１５と同様の処理を行った。(Example 18)
As Example 18, the same processing as in Examples 1 to 15 was performed except that each metal of the raw material had a composition as shown in Table 1 and firing was performed under a pressure of 120 KPa instead of atmospheric pressure.
（比較例１〜３）
比較例１〜３として、原料の各金属を表１に示すような組成とし、前駆体乾燥後の分級を行わず、且つ、最後の酸化物の解砕をメディアン径が１μｍ以下もしくは２０μｍ以上になるまで行った点以外は、実施例１〜１５と同様の処理を行った。(Comparative Examples 1-3)
As Comparative Examples 1 to 3, the raw materials have a composition as shown in Table 1, the classification after drying the precursor is not performed, and the final oxide is crushed to a median diameter of 1 μm or less or 20 μm or more. The same processing as in Examples 1 to 15 was performed except for the points performed until the end.
（比較例４〜７）
比較例４〜７として、原料の各金属を表１に示すような組成とし、酸素雰囲気炉ではなく空気雰囲気炉で焼成工程を行った点以外は、比較例１と同様の処理を行った。(Comparative Examples 4-7)
As Comparative Examples 4 to 7, the same processing as in Comparative Example 1 was performed, except that each metal of the raw material had a composition as shown in Table 1 and the firing step was performed in an air atmosphere furnace instead of an oxygen atmosphere furnace.
（評価）
−正極材組成の評価−
各正極材中の金属含有量は、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＯＥＳ）で測定し、各金属の組成比（モル比）を算出し、表１の通りとなったことを確認した。また、酸素含有量はＬＥＣＯ法で測定しαを算出した。(Evaluation)
-Evaluation of composition of positive electrode material-
The metal content in each positive electrode material was measured with an inductively coupled plasma optical emission spectrometer (ICP-OES), and the composition ratio (molar ratio) of each metal was calculated to confirm that it was as shown in Table 1. . The oxygen content was measured by the LECO method and α was calculated.
−メディアン径の評価−
各正極材の粉末を採取し、粒度分布のメディアン径をレーザー回折型粒度分布測定装置（島津製作所 ＳＡＬＤ−３０００）によって測定した。-Evaluation of median diameter-
The powder of each positive electrode material was sampled, and the median diameter of the particle size distribution was measured with a laser diffraction type particle size distribution measuring apparatus (Salazu Corporation SALD-3000).
−安息角の評価−
各正極材の粉末を採取し、ＪＩＳＺ ８８０１で規定された標準篩を振動させ、該標準篩へ粉体を投入した。標準篩を通った粉体をロートを通して水平なテーブル上へ落とした。このときの標準篩の振動幅は２ｍｍ、篩にかけた時間は４分間、ロートの口径は８ｍｍであった。
テーブル上に落下させた粉体の山に対して、安息角を測定した。安息角の測定は、半導体レーザー（波長６７０ｎｍ）の変位センサーによる角度計算方式（最小二乗法）を用いて行い、最小読み取り分解能は０．１度とした。-Evaluation of angle of repose-
The powder of each positive electrode material was collected, the standard sieve specified in JISZ 8801 was vibrated, and the powder was put into the standard sieve. The powder that passed through the standard sieve was dropped onto a horizontal table through a funnel. At this time, the vibration width of the standard sieve was 2 mm, the time applied to the sieve was 4 minutes, and the diameter of the funnel was 8 mm.
The angle of repose was measured on the pile of powder dropped on the table. The angle of repose was measured using an angle calculation method (least square method) using a semiconductor laser (wavelength 670 nm) displacement sensor, and the minimum reading resolution was 0.1 degree.
−比表面積の評価−
ＢＥＴ法による比表面積測定をおこなった。（ＪＩＳ−Ｚ−８８３０参照）。測定にはユアサ・アイオニクス社製流動法ＢＥＴ一点法比表面積測定装置ＭＯＮＯＳＯＲＢを用いた。-Evaluation of specific surface area-
Specific surface area was measured by the BET method. (See JIS-Z-8830). For the measurement, a flow method BET single point method specific surface area measuring device MONOSORB manufactured by Yuasa Ionics Co., Ltd. was used.
−電池特性の評価−
各正極材と、導電材と、バインダーとを８５：８：７の割合で秤量し、バインダーを有機溶媒（Ｎ−メチルピロリドン）に溶解したものに、正極材料と導電材とを混合してスラリー化し、Ａｌ箔上に塗布して乾燥後にプレスして正極とした。続いて、対極をＬｉとした評価用の２０３２型コインセルを作製し、電解液に１Ｍ−ＬｉＰＦ6をＥＣ−ＤＭＣ（１：１）に溶解したものを用いて、電流密度０．２Ｃの際の放電容量を測定した。また電流密度０．２Ｃのときの電池容量に対する電流密度２Ｃのときの、放電容量の比を算出してレート特性を得た。さらに、容量保持率は、室温で１Ｃの放電電流で得られた初期放電容量と１００サイクル後の放電容量を比較することによって測定した。
これらの結果を表１に示す。-Evaluation of battery characteristics-
Each positive electrode material, conductive material, and binder are weighed in a ratio of 85: 8: 7, and the positive electrode material and the conductive material are mixed into a slurry in which the binder is dissolved in an organic solvent (N-methylpyrrolidone). And coated on an Al foil, dried and pressed to obtain a positive electrode. Subsequently, a 2032 type coin cell for evaluation with Li as the counter electrode was prepared, and 1M-LiPF 6 dissolved in EC-DMC (1: 1) was used as the electrolyte, and the current density was 0.2C. The discharge capacity was measured. Further, a rate characteristic was obtained by calculating a ratio of the discharge capacity when the current density was 2C to the battery capacity when the current density was 0.2C. Furthermore, the capacity retention was measured by comparing the initial discharge capacity obtained with a 1 C discharge current at room temperature with the discharge capacity after 100 cycles.
These results are shown in Table 1.
Claims (11)
（前記式において、Ｍは必須成分としてのＣｏ、及び、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｕ、Ｚｎ、Ｇａ、Ｇｅ、Ａｌ、Ｂｉ、Ｓｎ、Ｍｇ、Ｃａ、Ｂ及びＺｒから選択される１種以上であり、０≦ｘ≦０．１であり、０＜ｙ≦０．７であり、α＞０である。）
で表され、
粒度分布のメディアン径が１〜２０μｍであって、安息角が８０°以下であるリチウムイオン電池用正極活物質。Composition formula: Li (Li x Ni 1- xy M y) O 2 + α
(In the above formula, M is selected from Co as an essential component and Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca, B, and Zr. 1 or more selected from the above, 0 ≦ x ≦ 0.1, 0 <y ≦ 0.7, and α> 0.)
Represented by
A positive electrode active material for a lithium ion battery having a median diameter of particle size distribution of 1 to 20 μm and an angle of repose of 80 ° or less.
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