JP2005225734A - Fluorine-containing lithium cobalt composite oxide and method for producing the same - Google Patents
Fluorine-containing lithium cobalt composite oxide and method for producing the same Download PDFInfo
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Abstract
【課題】 リチウムイオン二次電池のサイクル特性が向上し、また負荷特性が向上する正極活物質として有用なフッ素含有リチウムコバルト系複合酸化物を提供すること。
【解決手段】 本発明のフッ素含有リチウムコバルト系複合酸化物は、可溶性のフッ素原子の量が２０００ｐｐｍ以下であり、Ｆ／Ｃｏの原子比が０．０１以下であることを特徴とする。また、表面にアルカリ土類金属の酸化物が存在していることを特徴とする。また、（１１０）ベクトル方向の結晶子サイズが９５０Å以下である。コバルトの一部は遷移金属元素（但しマンガン及びニッケルを除く）で置換されていてもよい。
【選択図】 なし
PROBLEM TO BE SOLVED: To provide a fluorine-containing lithium cobalt composite oxide useful as a positive electrode active material in which cycle characteristics of a lithium ion secondary battery are improved and load characteristics are improved.
The fluorine-containing lithium cobalt composite oxide of the present invention is characterized in that the amount of soluble fluorine atoms is 2000 ppm or less and the F / Co atomic ratio is 0.01 or less. In addition, an alkaline earth metal oxide is present on the surface. The crystallite size in the (110) vector direction is 950 mm or less. A part of cobalt may be substituted with a transition metal element (except manganese and nickel).
[Selection figure] None
Description
本発明は、フッ素含有リチウムコバルト系複合酸化物及びその製造方法に関する。本発明のフッ素含有リチウムコバルト系複合酸化物は、リチウムイオン二次電池用の正極活物質として特に有用である。 The present invention relates to a fluorine-containing lithium cobalt composite oxide and a method for producing the same. The fluorine-containing lithium cobalt composite oxide of the present invention is particularly useful as a positive electrode active material for a lithium ion secondary battery.
リチウムイオン二次電池の正極活物質として用いられるリチウムコバルト系複合酸化物にフッ素を含有させて、電池の各種性能を向上させる提案が種々知られている。例えば高温下でのサイクル特性や保存安定性を高めることを目的として、リチウムコバルト系複合酸化物の表面をフッ化リチウムで被覆することが提案されている（特許文献１参照）。同様に高温下でのサイクル特性を高めることを目的として、合成時の焼成によりフッ化リチウムを添加し、且つフッ素の含有量をリチウムコバルト系複合酸化物全体に対して０．００１〜５重量％とすることも提案されている（特許文献２参照）。また高負荷時のサイクル特性を高めることを目的として、フッ素及びアルカリ土類金属を固溶させたリチウムコバルト系複合酸化物が提案されている（特許文献３参照）。 Various proposals for improving the various performances of a battery by incorporating fluorine into a lithium cobalt composite oxide used as a positive electrode active material of a lithium ion secondary battery are known. For example, for the purpose of improving cycle characteristics and storage stability at high temperatures, it has been proposed to coat the surface of a lithium cobalt-based composite oxide with lithium fluoride (see Patent Document 1). Similarly, for the purpose of enhancing cycle characteristics at high temperatures, lithium fluoride is added by firing during synthesis, and the fluorine content is 0.001 to 5% by weight based on the entire lithium cobalt composite oxide. Has also been proposed (see Patent Document 2). Further, for the purpose of enhancing cycle characteristics under high load, a lithium cobalt based composite oxide in which fluorine and alkaline earth metal are dissolved is proposed (see Patent Document 3).
また本出願人は先に、負荷特性、サイクル特性、高温保存特性、低温特性及び安全性に優れたリチウム二次電池の正極活物質として有用なリチウムコバルト系複合酸化物として、フッ素原子を０．０２５〜２．５重量％含有するリチウムコバルト系複合酸化物であって、該コバルト酸リチウム粒子の内部に存在するフッ素原子の量が全体の１０〜３０重量％であるものを提案した（特許文献４参照）。 In addition, the present applicant has previously described a fluorine atom as a lithium cobalt-based composite oxide useful as a positive electrode active material of a lithium secondary battery excellent in load characteristics, cycle characteristics, high temperature storage characteristics, low temperature characteristics and safety. A lithium-cobalt composite oxide containing 025 to 2.5 wt% was proposed in which the amount of fluorine atoms present in the lithium cobaltate particles was 10 to 30 wt% of the total (Patent Document) 4).
しかしリチウムイオン二次電池に要求される各種性能はますます高くなっており、前述したリチウムコバルト系複合酸化物よりも更に高性能のものが必要とされている。 However, various performances required for lithium ion secondary batteries are becoming higher and higher performance than the above-described lithium cobalt complex oxide is required.
従って本発明の目的は、前述した従来技術のリチウムコバルト系複合酸化物よりも更に高性能のフッ素含有リチウムコバルト系複合酸化物及びその製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a fluorine-containing lithium cobalt composite oxide having higher performance than the above-described prior art lithium cobalt composite oxide and a method for producing the same.
本発明は、可溶性のフッ素原子の量が２０００ｐｐｍ以下であり、Ｆ／Ｃｏの原子比が０．０１以下であることを特徴とするフッ素含有リチウムコバルト系複合酸化物を提供することにより前記目的を達成したものである。 The object of the present invention is to provide a fluorine-containing lithium cobalt composite oxide characterized in that the amount of soluble fluorine atoms is 2000 ppm or less and the atomic ratio of F / Co is 0.01 or less. Achieved.
また本発明は、表面にアルカリ土類金属の酸化物が存在していることを特徴とするフッ素含有リチウムコバルト系複合酸化物を提供するものである。 The present invention also provides a fluorine-containing lithium cobalt composite oxide characterized in that an alkaline earth metal oxide is present on the surface.
更に本発明は前記フッ素含有リチウムコバルト系複合酸化物の好ましい製造方法として、リチウム化合物、コバルト化合物及びフッ素化合物を、Ｌｉ原子に対するモル比で、Ｃｏ原子０．９〜１．１、Ｆ原子０．００１〜０．１５で添加して精密混合し、１０００℃以上で焼成を行い、且つリチウム化合物として平均粒径が５〜８μｍのものを用いることを特徴とするフッ素含有リチウムコバルト系複合酸化物の製造方法を提供するものである。 Further, in the present invention, as a preferred method for producing the fluorine-containing lithium cobalt composite oxide, a lithium compound, a cobalt compound, and a fluorine compound are mixed at a molar ratio with respect to Li atoms, Co atoms of 0.9 to 1.1, F atoms of 0.1. Fluorine-containing lithium cobalt based composite oxide characterized in that it is added at 001 to 0.15, precisely mixed, fired at 1000 ° C. or higher, and a lithium compound having an average particle diameter of 5 to 8 μm is used. A manufacturing method is provided.
本発明のフッ素含有リチウムコバルト系複合酸化物をリチウムイオン二次電池の正極活物質として用いると、非水電解液の分解が抑制され、リチウムイオン二次電池のサイクル特性が向上する。また負荷特性も向上する。非水電解液の分解が抑制されることは、リチウムイオン二次電池の充電電圧を高めて電池を高容量にしたい場合に特に有効である。 When the fluorine-containing lithium cobalt based composite oxide of the present invention is used as a positive electrode active material of a lithium ion secondary battery, decomposition of the non-aqueous electrolyte is suppressed and cycle characteristics of the lithium ion secondary battery are improved. Also, load characteristics are improved. Suppressing the decomposition of the non-aqueous electrolyte is particularly effective when it is desired to increase the charging voltage of the lithium ion secondary battery to increase the capacity of the battery.
以下、本発明をその好ましい実施形態に基づき説明する。本発明のフッ素含有リチウムコバルト系複合酸化物（以下、単にリチウムコバルト系複合酸化物ともいう）はＬｉＣｏＯ2を基本構造とし、更にフッ素を含有するものである。リチウムコバルト系複合酸化物は、可溶性のフッ素原子の量が２０００ｐｐｍ以下のものである。フッ素を含有するリチウムコバルト系複合酸化物は、これをリチウムイオン二次電池の正極活物質として用いると、非水電解液の分解を抑制し電池のサイクル特性低下を防止する効果があることが知られている。しかし、本発明者らの検討の結果、リチウムコバルト系複合酸化物における可溶性のフッ素原子の量が２０００ｐｐｍ超であると、リチウムコバルト系複合酸化物へのリチウムイオンの吸脱蔵の抵抗が大きくなってしまい、逆に電池のサイクル特性が低下してしまうことが判明した。この観点から可溶性のフッ素原子の量は２００〜２０００ｐｐｍであることが好ましく、３００〜１０００ｐｐｍであることが更に好ましい。リチウムコバルト系複合酸化物において可溶性のフッ素がどのような状態で存在しているかは明らかではないが、各種化合物の状態、例えばフッ化リチウムの状態で存在しているものと推測される。 Hereinafter, the present invention will be described based on preferred embodiments thereof. The fluorine-containing lithium cobalt composite oxide (hereinafter also simply referred to as lithium cobalt composite oxide) of the present invention has LiCoO 2 as a basic structure and further contains fluorine. The lithium cobalt composite oxide has a soluble fluorine atom amount of 2000 ppm or less. Fluorine-containing lithium-cobalt composite oxide is known to have the effect of suppressing degradation of the non-aqueous electrolyte and preventing deterioration of the cycle characteristics of the battery when used as a positive electrode active material of a lithium ion secondary battery. It has been. However, as a result of the study by the present inventors, when the amount of soluble fluorine atoms in the lithium cobalt composite oxide exceeds 2000 ppm, the resistance to absorption and desorption of lithium ions into the lithium cobalt composite oxide increases. On the contrary, it has been found that the cycle characteristics of the battery deteriorate. From this viewpoint, the amount of soluble fluorine atoms is preferably 200 to 2000 ppm, and more preferably 300 to 1000 ppm. Although it is not clear in what state soluble fluorine exists in the lithium cobalt complex oxide, it is presumed that it exists in the state of various compounds such as lithium fluoride.
リチウムコバルト系複合酸化物に含まれる可溶性のフッ素の量は、リチウムコバルト系複合酸化物を水に分散させ、溶出するフッ素原子の量をイオンクロマトグラフィーで定量分析することより測定する。この測定方法から明らかなように、本発明における可溶性フッ素の量とは、リチウムコバルト系複合酸化物の表面に存在するフッ素の量のことである。可溶性のフッ素の量を前記の値以下とするには、例えば後述する製造方法に従ってリチウムコバルト系複合酸化物を製造すればよい。 The amount of soluble fluorine contained in the lithium cobalt composite oxide is measured by dispersing the lithium cobalt composite oxide in water and quantitatively analyzing the amount of eluted fluorine atoms by ion chromatography. As is apparent from this measurement method, the amount of soluble fluorine in the present invention is the amount of fluorine present on the surface of the lithium cobalt composite oxide. In order to make the amount of soluble fluorine equal to or less than the above value, for example, a lithium cobalt composite oxide may be manufactured according to a manufacturing method described later.
可溶性のフッ素原子の量が前述の値以下であることに加えて、本発明のリチウムコバルト系複合酸化物は、Ｆ／Ｃｏの原子比（以下、Ｆ／Ｃｏ比という）が０．０１以下のものである。Ｆ／Ｃｏ比が０．０１超であると、リチウムコバルト系複合酸化物へのフッ素原子の固溶が顕著なものとなり、リチウムコバルト系複合酸化物表面での抵抗が上昇し、電池の負荷特性が低下してしまう。この観点から、Ｆ／Ｃｏ比は０．０００５〜０．０１であることが好ましく、０．００１〜０．００５であることが更に好ましい。Ｆ／Ｃｏ比の測定は、Ｆをイオンクロマト法で、Ｃｏをキレート滴定法で測定し、それらの測定結果から両者の比を求める。Ｆ／Ｃｏ比を前記の値以下とするには、例えば後述する製造方法に従ってリチウムコバルト系複合酸化物を製造すればよい。 In addition to the amount of soluble fluorine atoms being not more than the aforementioned value, the lithium cobalt composite oxide of the present invention has an F / Co atomic ratio (hereinafter referred to as F / Co ratio) of 0.01 or less. Is. When the F / Co ratio exceeds 0.01, the solid solution of fluorine atoms in the lithium cobalt composite oxide becomes remarkable, the resistance on the surface of the lithium cobalt composite oxide increases, and the load characteristics of the battery Will fall. From this viewpoint, the F / Co ratio is preferably 0.0005 to 0.01, and more preferably 0.001 to 0.005. In measuring the F / Co ratio, F is measured by ion chromatography and Co is measured by chelate titration, and the ratio between the two is determined from the measurement results. In order to make the F / Co ratio equal to or less than the above value, for example, a lithium cobalt composite oxide may be manufactured according to a manufacturing method described later.
本発明のリチウムコバルト系複合酸化物は、その表面にアルカリ土類金属の酸化物、例えば酸化マグネシウムや酸化カルシウムが存在している。そしてアルカリ土類金属は、リチウムコバルト系複合酸化物中に実質的に固溶していない。先に説明した特許文献３記載の技術では、リチウムコバルト系複合酸化物中にアルカリ土類金属を固溶させて、リチウムイオンの吸脱蔵に起因するリチウムコバルト系複合酸化物の体積変化を緩和しようとしている。これとは対照的に、本発明者らは、アルカリ土類金属の酸化物をリチウムコバルト系複合酸化物の表面に存在させることで、非水電解液の分解が抑制され電池のサイクル特性低下が防止されることを見出した。リチウムイオン二次電池の容量を高めるための一手段として、その充電電圧を、一般的な値である４．３Ｖから４．５Ｖへ引き上げることが知られている。この場合、非水電解液の分解が起こりやすくなるという不都合が生じる。しかし、アルカリ土類金属の酸化物をリチウムコバルト系複合酸化物の表面に存在させることで、充電電圧を引き上げても非水電解液の分解を防止できるという利点がある。 The lithium cobalt complex oxide of the present invention has an alkaline earth metal oxide such as magnesium oxide or calcium oxide on the surface thereof. The alkaline earth metal is not substantially dissolved in the lithium cobalt composite oxide. In the technology described in Patent Document 3 described above, alkaline earth metal is dissolved in the lithium cobalt composite oxide to reduce the volume change of the lithium cobalt composite oxide caused by the absorption and desorption of lithium ions. Trying to. In contrast, the present inventors have made alkaline earth metal oxides present on the surface of the lithium cobalt complex oxide, thereby suppressing the decomposition of the non-aqueous electrolyte and reducing the cycle characteristics of the battery. I found that it was prevented. As one means for increasing the capacity of a lithium ion secondary battery, it is known to increase the charging voltage from a general value of 4.3 V to 4.5 V. In this case, there arises a disadvantage that the non-aqueous electrolyte is easily decomposed. However, the presence of the alkaline earth metal oxide on the surface of the lithium cobalt composite oxide has an advantage that the decomposition of the non-aqueous electrolyte can be prevented even when the charging voltage is increased.
リチウムコバルト系複合酸化物の表面にアルカリ土類金属の酸化物が存在しているか否かは、Ｘ線回折測定によってアルカリ土類金属の酸化物の回折ピークが観測されるか否かで判断することができる。表面にアルカリ土類金属の酸化物が存在するリチウムコバルト系複合酸化物の製造方法については後述する。この製造方法によって得られるリチウムコバルト系複合酸化物は、リチウムコバルト系複合酸化物の製造後にアルカリ土類金属の酸化物を表面に付着させたものと比較して、サイクル特性低下の防止効果が全く相違する。つまり、アルカリ土類金属の酸化物が表面に存在している本発明のリチウムコバルト系複合酸化物は、リチウムコバルト系複合酸化物の製造後にアルカリ土類金属の酸化物を表面に付着させたものとは構造上明確に区別されるものであると考えられる。 Whether or not an alkaline earth metal oxide is present on the surface of the lithium cobalt complex oxide is determined by whether or not a diffraction peak of the alkaline earth metal oxide is observed by X-ray diffraction measurement. be able to. A method for producing a lithium cobalt composite oxide having an alkaline earth metal oxide on the surface will be described later. The lithium cobalt composite oxide obtained by this manufacturing method is completely less effective in preventing the deterioration of cycle characteristics as compared with the case where an alkaline earth metal oxide is adhered to the surface after the manufacture of the lithium cobalt composite oxide. Is different. That is, the lithium cobalt complex oxide of the present invention in which an alkaline earth metal oxide is present on the surface is obtained by depositing an alkaline earth metal oxide on the surface after the production of the lithium cobalt complex oxide. Is considered to be clearly distinguished from the structure.
本発明のリチウムコバルト系複合酸化物においては、その結晶構造における（１１０）ベクトル方向の結晶子サイズが９５０Å以下であることが好ましい。これによってサイクル特性が一層向上する。（１１０）ベクトル方向の結晶子サイズは、リチウムコバルト系複合酸化物のＸ線回折測定によって得られる（１１０）ベクトル方向のピークの半値幅から求めることができる。サイクル特性を更に一層向上させる観点から、前記の結晶子サイズは７５０Å〜９５０Åであることが更に好ましく、８００〜９００Åであることが特に好ましい。結晶子サイズを前記の値以下とするためには、例えば後述する製造方法に従ってリチウムコバルト系複合酸化物を製造すればよい。 In the lithium cobalt composite oxide of the present invention, the crystallite size in the (110) vector direction in the crystal structure is preferably 950Å or less. This further improves cycle characteristics. The crystallite size in the (110) vector direction can be obtained from the half-value width of the peak in the (110) vector direction obtained by X-ray diffraction measurement of the lithium cobalt composite oxide. From the viewpoint of further improving the cycle characteristics, the crystallite size is more preferably from 750 to 950, and particularly preferably from 800 to 900. In order to make the crystallite size equal to or smaller than the above value, for example, a lithium cobalt composite oxide may be manufactured according to a manufacturing method described later.
本発明のリチウムコバルト系複合酸化物は、コバルトの一部が遷移金属元素（但しマンガン及びニッケルを除く）で置換されていてもよい。これによって該酸化物の構造が安定化し、リチウムイオン二次電池の充電電圧を上昇させてもサイクル特性が低下することを防止することができる。置換可能な遷移金属としては、ジルコニウム、チタン、バナジウム、クロム、鉄などが挙げられる。これらの遷移金属のうち、サイクル特性を一層向上させ得る観点からジルコニウムやチタンを用いることが好ましい。 In the lithium cobalt based composite oxide of the present invention, a part of cobalt may be substituted with a transition metal element (except manganese and nickel). As a result, the structure of the oxide is stabilized, and deterioration of cycle characteristics can be prevented even when the charging voltage of the lithium ion secondary battery is increased. Examples of substitutable transition metals include zirconium, titanium, vanadium, chromium, and iron. Of these transition metals, it is preferable to use zirconium or titanium from the viewpoint of further improving the cycle characteristics.
遷移元素の置換量は、Ｍ／Ｃｏの原子比（Ｍは遷移金属を表す）が０．００１〜０．０１、特に０．００１〜０．００５であることが好ましい。 The substitution amount of the transition element is preferably such that the M / Co atomic ratio (M represents a transition metal) is 0.001 to 0.01, particularly 0.001 to 0.005.
次に、本発明のリチウムコバルト系複合酸化物の好ましい製造方法について説明する。本発明の製造方法においては、先ずリチウム化合物、コバルト化合物及びフッ素化合物の三者を添加する。三者の添加割合は、Ｌｉ原子に対するモル比で、Ｃｏ原子が０．９〜１．１、特に０．９５〜１．０５となるようにする。またＬｉ原子に対するモル比で、Ｆ原子が０．００１〜０．１５、特に０．００２〜０．１となるようにする。この配合割合で後述する焼成を行うことにより、得られるリチウムコバルト系複合酸化物を正極活物質として用いたリチウム二次電池は、特に負荷特性、サイクル特性（４．３Ｖ及び４．５Ｖ）に優れたものとなる。 Next, a preferred method for producing the lithium cobalt composite oxide of the present invention will be described. In the production method of the present invention, first, a lithium compound, a cobalt compound and a fluorine compound are added. The addition ratio of the three elements is such that the Co atom is 0.9 to 1.1, particularly 0.95 to 1.05 in terms of a molar ratio to Li atoms. Further, the F atoms are set to 0.001 to 0.15, particularly 0.002 to 0.1, in a molar ratio to Li atoms. By performing the firing described later at this blending ratio, the lithium secondary battery using the obtained lithium cobalt composite oxide as the positive electrode active material is particularly excellent in load characteristics and cycle characteristics (4.3 V and 4.5 V). It will be.
リチウム化合物としては炭酸リチウム、水酸化リチウム、硝酸リチウム、塩化リチウム、硫酸リチウム等の無機リチウム塩、酢酸リチウム等の有機リチウム塩、及びリチウムアセチルアセタート等のリチウム含有錯体化合物などを用いることができる。工業的に入手しやすく、また安価であることから炭酸リチウムを用いることが好ましい。コバルト化合物としては、炭酸コバルト、四酸化三コバルト、三酸化二コバルト、オキシ水酸化コバルトなどを用いることができる。フッ素化合物としては、フッ化リチウム、フッ化マグネシウム、フッ化ニッケル、フッ化カルシウム、フッ化亜鉛等が挙げられる。これらの各種化合物のうち、リチウム化合物として炭酸リチウムを用い、コバルト化合物として四酸化三コバルトを用い、フッ素化合物としてフッ化マグネシウム又はフッ化カルシウムを用いることが好ましい。これによって、アルカリ土類金属であるマグネシウムやカルシウムの酸化物を、リチウムコバルト系複合酸化物の表面に存在させることができる。これに対して、先に説明した特許文献３記載の技術のように、リチウム源及びフッ素源としてフッ化リチウムを用い、更に炭酸マグネシウムを用いても、リチウムコバルト系複合酸化物の表面にアルカリ土類金属（ここではマグネシウム）の酸化物を存在させることはできない。 As the lithium compound, inorganic lithium salts such as lithium carbonate, lithium hydroxide, lithium nitrate, lithium chloride, and lithium sulfate, organic lithium salts such as lithium acetate, and lithium-containing complex compounds such as lithium acetyl acetate can be used. . Lithium carbonate is preferably used because it is easily available industrially and is inexpensive. As the cobalt compound, cobalt carbonate, tricobalt tetroxide, dicobalt trioxide, cobalt oxyhydroxide, or the like can be used. Examples of the fluorine compound include lithium fluoride, magnesium fluoride, nickel fluoride, calcium fluoride, and zinc fluoride. Of these various compounds, lithium carbonate is preferably used as the lithium compound, tricobalt tetroxide is used as the cobalt compound, and magnesium fluoride or calcium fluoride is preferably used as the fluorine compound. Thereby, an oxide of magnesium or calcium, which is an alkaline earth metal, can be present on the surface of the lithium cobalt composite oxide. On the other hand, even if lithium fluoride is used as the lithium source and fluorine source and magnesium carbonate is used as in the technique described in Patent Document 3 described above, alkaline earth is not formed on the surface of the lithium cobalt composite oxide. An oxide of a similar metal (here magnesium) cannot be present.
リチウム化合物は、その平均粒径が５〜８μｍ、特に６〜７μｍのものを用いることが好ましい。これによってコバルト化合物との精密な混合を行う事ができるという有利な効果が奏されるからである。リチウム化合物の平均粒径はレーザー法粒度分布測定装置によって測定される。 A lithium compound having an average particle diameter of 5 to 8 μm, particularly 6 to 7 μm is preferably used. This is because an advantageous effect that precise mixing with the cobalt compound can be achieved. The average particle size of the lithium compound is measured by a laser particle size distribution analyzer.
次に、リチウム化合物、コバルト化合物及びフッ素化合物の三者は所定手段によって混合される。混合は、乾式又は湿式の何れの方法でもよい。製造が容易であることから乾式混合が好ましい。乾式混合の場合、精密混合を行うことが特に好ましい。本発明で精密混合とは、高エネルギーの機械力を加えて混合することをいう。具体的には、混合機として羽根が内部で回転する事のできる混合機を用い、その撹拌羽根の周速が４０ｍ／ｓ以上となるような高エネルギーの機械力を加える。この精密混合及び後述する焼成温度の制御によって、可溶性フッ素原子の量及びＦ／Ｃｏ比をコントロールすることができる。また、結晶子サイズをコントロールすることができる。 Next, the lithium compound, cobalt compound, and fluorine compound are mixed by a predetermined means. Mixing may be either dry or wet. Dry mixing is preferred because it is easy to produce. In the case of dry mixing, it is particularly preferable to carry out precision mixing. In the present invention, the precision mixing means mixing by applying a high energy mechanical force. Specifically, a mixer in which blades can rotate inside is used as a mixer, and a high energy mechanical force is applied so that the peripheral speed of the stirring blade is 40 m / s or more. The amount of soluble fluorine atoms and the F / Co ratio can be controlled by this precise mixing and controlling the firing temperature described later. In addition, the crystallite size can be controlled.
精密混合の時間に特に制限はない。概ね０．２〜０．５時間混合を行えば十分である。 There is no particular limitation on the precision mixing time. It is sufficient to mix for approximately 0.2 to 0.5 hours.
精密混合によって得られた混合物は次いで焼成工程に付される。焼成温度は好ましくは１０００℃以上、更に好ましくは１０２０℃以上、一層好ましくは１０３０℃以上である。焼成温度が１０００℃未満では、詳細な理由は不明であるが、本発明の効果であるサイクル特性及び負荷特性の向上が見られない。焼成時間は２〜２４時間、特に５〜１０時間とすることが好ましい。焼成は、大気中又は酸素雰囲気中のいずれで行ってもよい。焼成は必要により何度でも行うことができる。 The mixture obtained by precision mixing is then subjected to a firing step. The firing temperature is preferably 1000 ° C. or higher, more preferably 1020 ° C. or higher, and still more preferably 1030 ° C. or higher. When the firing temperature is less than 1000 ° C., the detailed reason is unknown, but the cycle characteristics and load characteristics, which are the effects of the present invention, are not improved. The firing time is preferably 2 to 24 hours, particularly 5 to 10 hours. Firing may be performed in the air or in an oxygen atmosphere. Firing can be performed as many times as necessary.
また焼成は、得られるリチウムコバルト系複合酸化物における炭酸リチウムの含有量が０．０５重量％以下、特に０．０３重量％以下となるように行われることが好ましい。焼成により得られるリチウムコバルト系複合酸化物に炭酸リチウムが前記の値を超えて含まれていると、負荷特性が低下しやすいからである。この理由から明らかなように、炭酸リチウムの含有量は０に近ければ近いほど好ましい。 The firing is preferably performed so that the lithium carbonate content in the obtained lithium cobalt composite oxide is 0.05% by weight or less, particularly 0.03% by weight or less. This is because if the lithium cobalt composite oxide obtained by firing contains lithium carbonate in excess of the above value, the load characteristics are likely to deteriorate. As is clear from this reason, the closer the content of lithium carbonate is to 0, the better.
更に焼成は、得られるリチウムコバルト系複合酸化物における四酸化三コバルトの含有量が０．０５〜３重量％、特に０．１〜１重量％となるように行われることが好ましい。焼成により得られるリチウムコバルト系複合酸化物に四酸化三コバルトが前記の範囲外含まれていると、負荷特性の低下が起こりやすく、また容量の低下も起こりやすいからである。 Further, the firing is preferably performed so that the content of tricobalt tetroxide in the obtained lithium cobalt-based composite oxide is 0.05 to 3% by weight, particularly 0.1 to 1% by weight. This is because, if the lithium cobalt-based composite oxide obtained by firing contains tricobalt tetroxide outside the above range, the load characteristics are likely to be lowered and the capacity is likely to be lowered.
リチウムコバルト系複合酸化物における炭酸リチウム及び四酸化三コバルトの含有量はそれぞれ次のようにして測定することができる。炭酸リチウムの含有量は、リチウムコバルト系複合酸化物を水に分散させた後、濾紙で濾過しその濾液を０．1ＮのＨＣｌで滴定し定量する。四酸化三コバルトの含有量は、リチウムコバルト系複合酸化物をＸ線回折測定し、２θ＝３８°付近の四酸化三コバルトのメインピークから算出する。 The contents of lithium carbonate and tricobalt tetroxide in the lithium cobalt composite oxide can be measured as follows. The content of lithium carbonate is determined by dispersing lithium cobalt composite oxide in water, filtering with a filter paper, and titrating the filtrate with 0.1N HCl. The content of tricobalt tetroxide is calculated from the main peak of tricobalt tetroxide near 2θ = 38 ° by X-ray diffraction measurement of the lithium cobalt complex oxide.
焼成後は適宜冷却し、必要に応じ粉砕して本発明のリチウムコバルト系複合酸化物を得る。このようにして得られたリチウムコバルト系複合酸化物は、前述した特性を有するので、これをリチウムイオンニ次電池の正極活物質として用いると、負荷特性とサイクル特性（４．３Ｖ及び４．５Ｖ）に優れた電池を得ることができ、極めて有用である。 After firing, the mixture is appropriately cooled and ground as necessary to obtain the lithium cobalt composite oxide of the present invention. The lithium cobalt based composite oxide thus obtained has the above-described characteristics. Therefore, when it is used as a positive electrode active material for a lithium ion secondary battery, load characteristics and cycle characteristics (4.3 V and 4.5 V) Can be obtained, and is extremely useful.
リチウムイオン二次電池は、正極、負極、セパレータ及びリチウム塩を含有する非水電解液を有している。正極は、例えば、正極集電体上に正極合剤を塗布乾燥等して形成されるものである。正極合剤は、本発明のフッ素含有リチウムコバルト系複合酸化物からなる正極活物質、カーボンブラック等の導電剤、ポリフッ化ビニリデンやポリビニルアルコールなどの結着剤、及び必要により添加されるフィラー等を含むものである。 The lithium ion secondary battery has a non-aqueous electrolyte containing a positive electrode, a negative electrode, a separator, and a lithium salt. The positive electrode is formed, for example, by applying and drying a positive electrode mixture on a positive electrode current collector. The positive electrode mixture includes a positive electrode active material comprising the fluorine-containing lithium cobalt composite oxide of the present invention, a conductive agent such as carbon black, a binder such as polyvinylidene fluoride and polyvinyl alcohol, and a filler added as necessary. Is included.
負極は、負極集電体上に炭素質材料等からなる負極活物質を塗布乾燥等して形成される。セパレータとしては、大きなイオン透過度を持ち、所定の機械的強度を持った絶縁性の薄膜が用いられる。例えばポリエチレンやポリプロピレンなどのオレフィン系ポリマー、ガラス繊維などからつくられたシートや不織布が用いられる。非水電解液としては、例えば、Ｎ−メチル−２−ピロリジノン、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネートなどが用いられる。リチウム塩としては、前記非水電解液に溶解するものが用いられ、例えば、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＣＦ3ＳＯ3などが挙げられる。リチウム二次電池に用いられるこれら材料は当業者に公知であり、これ以上の詳しい説明は要しない。その詳細については、例えば本出願人の先の出願に係る特開２００１−１２２６２６号公報の段落００３２〜００４３に記載されている。 The negative electrode is formed by applying and drying a negative electrode active material made of a carbonaceous material or the like on a negative electrode current collector. As the separator, an insulating thin film having a large ion permeability and a predetermined mechanical strength is used. For example, a sheet or non-woven fabric made from an olefin polymer such as polyethylene or polypropylene, glass fiber or the like is used. As the non-aqueous electrolyte, for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate and the like are used. As the lithium salt, those dissolved in the non-aqueous electrolyte are used, and examples thereof include LiClO 4 , LiBF 4 , LiPF 6 , and LiCF 3 SO 3 . These materials used for lithium secondary batteries are known to those skilled in the art, and no further detailed description is required. Details thereof are described, for example, in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2001-122626 relating to the earlier application of the present applicant.
以下に実施例を挙げて本発明を具体的に説明する。特に断らない限り「％」は「重量％」を意味する。 The present invention will be specifically described below with reference to examples. Unless otherwise specified, “%” means “% by weight”.
〔実施例１〕
炭酸リチウム、四酸化三コバルト、フッ化マグネシウムを、原子比Ｌｉ：Ｃｏ：Ｆ＝１：１：０．０１となるように計量した。炭酸リチウムの平均粒径は６．５μｍであった。これら三者を乳鉢に入れ均一に混合した。更に、ヘンシュルミキサーを用いて精密混合した。このとき撹拌羽根の周速を４０ｍ／ｓとした。０．５時間精密混合した後、混合原料をアルミナ製坩堝にいれ、大気下、１０３０℃で１０時間焼成した。焼成後に粉砕及び分級を行いフッ素含有リチウムコバルト系複合酸化物を得た。
[Example 1]
Lithium carbonate, tricobalt tetroxide, and magnesium fluoride were weighed so that the atomic ratio was Li: Co: F = 1: 1: 0.01. The average particle size of lithium carbonate was 6.5 μm. These three were placed in a mortar and mixed uniformly. Furthermore, precision mixing was performed using a Henshur mixer. At this time, the peripheral speed of the stirring blade was set to 40 m / s. After 0.5 hour precision mixing, the mixed raw material was put in an alumina crucible and baked at 1030 ° C. for 10 hours in the atmosphere. After firing, pulverization and classification were performed to obtain a fluorine-containing lithium cobalt composite oxide.
〔実施例２〕
炭酸リチウム、四酸化三コバルト、フッ化カルシウムを、原子比Ｌｉ：Ｃｏ：Ｆ＝１：１：０．０１となるように計量して用いる以外は実施例１と同様にしてフッ素含有リチウムコバルト系複合酸化物を得た。
[Example 2]
Fluorine-containing lithium cobalt system in the same manner as in Example 1 except that lithium carbonate, tricobalt tetroxide, and calcium fluoride are used in an atomic ratio of Li: Co: F = 1: 1: 0.01. A composite oxide was obtained.
〔実施例３〕
炭酸リチウム、四酸化三コバルト、フッ化マグネシウム、フッ化カルシウムを、原子比Ｌｉ：Ｃｏ：Ｆ＝１：１：０．０１で且つＣａ：Ｍｇ＝１：１となるように計量して用いる以外は実施例１と同様にしてフッ素含有リチウムコバルト系複合酸化物を得た。
Example 3
Lithium carbonate, tricobalt tetroxide, magnesium fluoride, and calcium fluoride are used in an atomic ratio of Li: Co: F = 1: 1: 0.01 and Ca: Mg = 1: 1. Obtained a fluorine-containing lithium cobalt composite oxide in the same manner as in Example 1.
〔比較例１〕
炭酸リチウム、四酸化三コバルト、フッ化マグネシウムを、原子比Ｌｉ：Ｃｏ：Ｆ＝１：１：０．０２となるように計量して用いる以外は実施例１と同様にしてフッ素含有リチウムコバルト系複合酸化物を得た。
[Comparative Example 1]
Fluorine-containing lithium cobalt system in the same manner as in Example 1, except that lithium carbonate, tricobalt tetroxide, and magnesium fluoride are used in an atomic ratio of Li: Co: F = 1: 1: 0.02. A composite oxide was obtained.
〔比較例２〕
炭酸リチウム、四酸化三コバルト、フッ化カルシウムを、原子比Ｌｉ：Ｃｏ：Ｆ＝１：１：０．０２となるように計量して用いる以外は実施例１と同様にしてフッ素含有リチウムコバルト系複合酸化物を得た。
[Comparative Example 2]
Fluorine-containing lithium cobalt system in the same manner as in Example 1 except that lithium carbonate, tricobalt tetroxide, and calcium fluoride are used in an atomic ratio of Li: Co: F = 1: 1: 0.02. A composite oxide was obtained.
〔比較例３〕
炭酸リチウム、四酸化三コバルト、フッ化マグネシウムを、原子比Ｌｉ：Ｃｏ：Ｆ＝１．２：１：０．０１となるように計量して用いる以外は実施例１と同様にしてフッ素含有リチウムコバルト系複合酸化物を得た。
[Comparative Example 3]
Fluorine-containing lithium in the same manner as in Example 1 except that lithium carbonate, tricobalt tetroxide, and magnesium fluoride were used in an atomic ratio of Li: Co: F = 1.2: 1: 0.01. A cobalt-based composite oxide was obtained.
〔比較例４〕
焼成温度を９５０℃とする以外は実施例１と同様にしてフッ素含有リチウムコバルト系複合酸化物を得た。
[Comparative Example 4]
A fluorine-containing lithium cobalt composite oxide was obtained in the same manner as in Example 1 except that the firing temperature was 950 ° C.
〔比較例５〕
乳鉢による混合後に精密混合を行わない以外は実施例１と同様にしてフッ素含有リチウムコバルト系複合酸化物を得た。
[Comparative Example 5]
A fluorine-containing lithium cobalt composite oxide was obtained in the same manner as in Example 1 except that precise mixing was not performed after mixing in the mortar.
〔比較例６〕
平均粒径１５μｍの炭酸リチウムを用いる以外は実施例１と同様にしてフッ素含有リチウムコバルト系複合酸化物を得た。
[Comparative Example 6]
A fluorine-containing lithium cobalt composite oxide was obtained in the same manner as in Example 1 except that lithium carbonate having an average particle size of 15 μm was used.
〔性能評価〕
各実施例及び比較例で得られたフッ素含有リチウムコバルト系複合酸化物について、前述した方法で可溶性のフッ素原子の量、Ｆ／Ｃｏ比、炭酸リチウムの含有量、四酸化三コバルトの含有量及び結晶子サイズを測定した。その結果を以下の表１に示す。また、得られたリチウムコバルト系複合酸化物を正極活物質として用いたリチウムイオン二次電池を作製し、以下の方法で、４．３充電時及び４．５Ｖ充電時の初期放電容量、容量維持率、初期エネルギー密度、エネルギー密度維持率を測定した。更に、１Ｃの放電容量及び１Ｃのエネルギー密度を測定した。これらの結果を以下の表２ないし４に示す。
[Performance evaluation]
About the fluorine-containing lithium cobalt-based composite oxide obtained in each Example and Comparative Example, the amount of fluorine atoms soluble in the above-described method, the F / Co ratio, the content of lithium carbonate, the content of tricobalt tetroxide and The crystallite size was measured. The results are shown in Table 1 below. In addition, a lithium ion secondary battery using the obtained lithium cobalt based composite oxide as a positive electrode active material was prepared, and the initial discharge capacity and capacity maintenance during 4.3 charging and 4.5 V charging were performed by the following method. The rate, initial energy density, and energy density maintenance rate were measured. Furthermore, the discharge capacity of 1C and the energy density of 1C were measured. These results are shown in Tables 2 to 4 below.
〔リチウムイオン二次電池の作製〕
各実施例及び比較例で得られたフッ素含有リチウムコバルト系複合酸化物９１％、黒鉛粉末６％、ポリフッ化ビニリデン３％を混合して正極合剤とし、これをＮ−メチル−２−ピロリジノンに分散させて混練ペーストを調製した。該混練ペーストをアルミ箔に塗布したのち、乾燥、プレスし、更に直径１５ｍｍの円盤に打ち抜いて正極板を得た。この正極板を用い、更にセパレーター、負極、正極、集電板、取り付け金具、外部端子、電解液等の各部材を使用してリチウムイオン二次電池を作製した。このうち、負極は金属リチウム箔を用い、電解液にはエチレンカーボネートとメチルエチルカーボネートの１：１混練液１リットルにＬｉＰＦ6１モルを溶解したものを使用した。
[Production of lithium ion secondary battery]
91% fluorine-containing lithium cobalt composite oxide, 6% graphite powder, and 3% polyvinylidene fluoride obtained in each example and comparative example were mixed to form a positive electrode mixture, which was converted into N-methyl-2-pyrrolidinone. A kneaded paste was prepared by dispersing. The kneaded paste was applied to an aluminum foil, dried and pressed, and then punched into a disk having a diameter of 15 mm to obtain a positive electrode plate. Using this positive electrode plate, a lithium ion secondary battery was produced using each member such as a separator, a negative electrode, a positive electrode, a current collector plate, a mounting bracket, an external terminal, and an electrolytic solution. Among these, a metal lithium foil was used for the negative electrode, and 1 mol of LiPF 6 dissolved in 1 liter of a 1: 1 kneaded solution of ethylene carbonate and methyl ethyl carbonate was used for the electrolyte.
〔初期放電容量及び初期エネルギー密度の測定〕
室温にて正極に対して定電流電圧（ＣＣＣＶ）０．５Ｃで４．３Ｖ又は４．５Ｖまで充電した後、０．２Ｃで２．７Ｖまで放電させる充放電を１サイクルとして、初期放電容量及び初期エネルギー密度を測定した。
[Measurement of initial discharge capacity and initial energy density]
Charging / discharging to positive electrode at a constant current voltage (CCCV) 0.5C at room temperature to 4.3V or 4.5V at room temperature and then discharging to 0.2V at 0.2C as one cycle, initial discharge capacity and The initial energy density was measured.
〔容量維持率及びエネルギー密度維持率の測定〕
前記の放電容量及びエネルギー密度の測定における充放電を２０サイクル行い、２０サイクル後の容量維持率及びエネルギー密度維持率を算出した。
[Measurement of capacity maintenance rate and energy density maintenance rate]
Charging / discharging in the measurement of the discharge capacity and energy density was performed 20 cycles, and the capacity retention rate and energy density retention rate after 20 cycles were calculated.
〔１Ｃの放電容量及び１Ｃのエネルギー密度〕
まず、正極に対して定電流電圧（ＣＣＣＶ）充電により０．５Ｃで５時間かけて、４．３Ｖまで充電した。次いで放電レート０．２Ｃ、０．５Ｃ、１．０Ｃで２．７Ｖまで放電させる充放電を行った。これらの操作を１サイクルとして１サイクル毎に放電容量とエネルギー密度を測定した。このサイクルを３サイクル繰り返し、３サイクル目の放電容量とエネルギー密度を求め、その値を１Ｃの放電容量及び１Ｃのエネルギー密度とした。なお、エネルギー密度はその値が高い方が、高負荷放電時でもより多くのエネルギーを利用でき、同じ放電容量の場合には一層高電圧での放電が可能であることを意味する。即ち負荷特性が優れていることを意味する。
[1C discharge capacity and 1C energy density]
First, the positive electrode was charged to 4.3 V by constant current voltage (CCCV) charging at 0.5 C for 5 hours. Next, charging / discharging was performed to discharge to 2.7 V at discharge rates of 0.2 C, 0.5 C, and 1.0 C. With these operations as one cycle, the discharge capacity and energy density were measured for each cycle. This cycle was repeated three times, and the discharge capacity and energy density of the third cycle were determined, and the values were taken as 1C discharge capacity and 1C energy density. A higher energy density means that more energy can be used even during high-load discharge, and discharge with a higher voltage is possible with the same discharge capacity. That is, it means that the load characteristic is excellent.
表１ないし表４に示す結果から明らかなように、各実施例で得られたリチウムコバルト系複合酸化物を正極活物質として用いたリチウムイオン二次電池は、放電容量及びエネルギー密度が高く、且つ２０サイクル後の維持率も高いことが判る。つまり、サイクル特性が高いことが判る。なお、表には示していないが、Ｘ線回折測定の結果、各実施例で得られたフッ素含有リチウムコバルト系複合酸化物においては、粒子の表面に酸化マグネシウム及び／又は酸化カルシウムが存在していることが確認された。 As is clear from the results shown in Tables 1 to 4, the lithium ion secondary battery using the lithium cobalt composite oxide obtained in each example as a positive electrode active material has a high discharge capacity and energy density, and It can be seen that the maintenance rate after 20 cycles is also high. That is, it can be seen that the cycle characteristics are high. Although not shown in the table, as a result of X-ray diffraction measurement, in the fluorine-containing lithium cobalt composite oxide obtained in each example, magnesium oxide and / or calcium oxide is present on the surface of the particles. It was confirmed that
Claims (10)
リチウム化合物、コバルト化合物及びフッ素化合物を、Ｌｉ原子に対するモル比で、Ｃｏ原子０．９〜１．１、Ｆ原子０．００１〜０．１５で添加して精密混合し、１０００℃以上で焼成を行い、且つリチウム化合物として平均粒径が５〜８μｍのものを用いることを特徴とするフッ素含有リチウムコバルト系複合酸化物の製造方法。 A method for producing the fluorine-containing lithium cobalt composite oxide according to claim 1,
Lithium compound, cobalt compound, and fluorine compound are added at a molar ratio of Li atom at a Co atom of 0.9 to 1.1 and F atom of 0.001 to 0.15, precisely mixed, and baked at 1000 ° C. or higher. And producing a fluorine-containing lithium cobalt composite oxide, wherein the lithium compound has an average particle size of 5 to 8 μm.
10. The production method according to claim 9, wherein lithium carbonate is used as the lithium compound, tricobalt tetroxide is used as the cobalt compound, and magnesium fluoride or calcium fluoride is used as the fluorine compound.
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