JP7043076B2 - Lithium-nickel-based composite oxide and its manufacturing method - Google Patents
Lithium-nickel-based composite oxide and its manufacturing method Download PDFInfo
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- 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
本発明は、リチウムニッケル系複合酸化物及びその製造方法に関する。 The present invention relates to a lithium nickel-based composite oxide and a method for producing the same.
リチウム含有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用いられている。リチウムイオン二次電池は、携帯電話、ノートパソコン用電源に使用されるだけでなく、車載用、電力負荷平準化システム用などの中型・大型電源用としても期待されており、一部実用化がなされている。 Lithium-containing composite oxides are used as positive electrode active materials for lithium ion secondary batteries. Lithium-ion secondary batteries are expected not only to be used as power sources for mobile phones and laptop computers, but also for medium-sized and large-sized power sources such as those for in-vehicle use and power load leveling systems, and some of them have been put into practical use. It has been done.
リチウム含有複合酸化物の中でもニッケル酸リチウムは、高い比容量（２００ｍＡｈ／ｇ）を有する４Ｖ級正極材料として期待されている。しかしながら、ニッケル酸リチウムは、高容量を得るために高い電圧（上限電圧：４．３Ｖ）以上まで充電するとサイクル特性が著しく劣化することが知られている。 Among the lithium-containing composite oxides, lithium nickelate is expected as a 4V class positive electrode material having a high specific volume (200 mAh / g). However, it is known that the cycle characteristics of lithium nickelate are significantly deteriorated when charged to a high voltage (upper limit voltage: 4.3 V) or higher in order to obtain a high capacity.
このような中、本発明者らは、特定の結晶構造を有し、かつ特定のパラメータを有するリチウム複合金属酸化物が、高容量を維持しつつ、サイクル特性の劣化を抑制することを見出している（下記特許文献１参照）。 Under these circumstances, the present inventors have found that a lithium composite metal oxide having a specific crystal structure and a specific parameter suppresses deterioration of cycle characteristics while maintaining a high capacity. (See Patent Document 1 below).
しかしながら、車載用などの長寿命が要求される用途においては、サイクル特性の劣化がさらに抑制された材料が必要である。 However, in applications where a long life is required, such as for automobiles, a material in which deterioration of cycle characteristics is further suppressed is required.
本発明は上記した従来技術の現状に鑑みてなされたものであり、高容量を有し、かつサイクル特性の劣化が顕著に抑制されたリチウム含有複合酸化物を提供することを目的とする。 The present invention has been made in view of the above-mentioned current state of the prior art, and an object of the present invention is to provide a lithium-containing composite oxide having a high capacity and significantly suppressed deterioration of cycle characteristics.
本発明者らは上記した目的を達成すべく鋭意研究を重ねた結果、驚くべきことに、特定の組成を有するリチウムニッケル系複合酸化物が、高容量を有し、かつサイクル特性の劣化が顕著に抑制されることを見出した。本発明者らは、かかる知見に基づきさらなる研究を重ねることにより、本発明を完成させるに至った。 As a result of diligent research to achieve the above-mentioned object, the present inventors surprisingly find that the lithium nickel-based composite oxide having a specific composition has a high capacity and the cycle characteristics are significantly deteriorated. It was found that it was suppressed. The present inventors have completed the present invention by repeating further research based on such findings.
即ち、本発明は、以下の項に記載の発明を包含する。
項１．一般式（１）：
ＬｉｘＮｉＯ２＋δ （１）
［式中、ｘは０．８≦ｘ≦１．３を示し、δは－０．２０≦δ≦０．２０を示す。］
で表されるリチウムニッケル系複合酸化物であって、
六方晶層状岩塩型構造の結晶相を含み、
格子定数ｃが１４．１３０Å以上１４．１９０未満である、リチウムニッケル系複合酸化物。
項２．格子体積が１００．００Å３以上１００．５０Å３未満である、上記項１に記載のリチウムニッケル系複合酸化物。
項３．六方晶層状岩塩型構造の結晶相のみからなる、上記項１又は２に記載のリチウムニッケル系複合酸化物。
項４．上記項１～３のいずれかに記載のリチウムニッケル系複合酸化物の製造方法であって、
水性溶媒中で、リチウム化合物と、水酸化ニッケル及び／又は水溶性ニッケル塩とを混合する第１工程、及び
前記第１工程により得られた混合物を酸化性雰囲気下で焼成する第２工程
を含む、製造方法。
項５．前記第１工程が、リチウム化合物を含む水溶液に水酸化ニッケル及び／又は水溶性ニッケル塩を添加する工程である、上記項４に記載の製造方法。
項６．前記第２工程における焼成温度が６００℃以上６９０℃以下である、上記項４又は５に記載の製造方法。
項７．上記項１～３のいずれかに記載のリチウムニッケル系複合酸化物を含む、リチウムイオン二次電池用正極材料。
項８．上記項７に記載のリチウムイオン二次電池用正極材料を含む、リチウムイオン二次電池。That is, the present invention includes the inventions described in the following sections.
Item 1. General formula (1):
Li x NiO 2 + δ (1)
[In the equation, x indicates 0.8 ≦ x ≦ 1.3, and δ indicates −0.20 ≦ δ ≦ 0.20. ]
It is a lithium nickel-based composite oxide represented by
Containing a crystalline phase of hexagonal layered rock salt type structure,
A lithium nickel-based composite oxide having a lattice constant c of 14.130 Å or more and less than 14.190.
Item 4. The method for producing a lithium nickel-based composite oxide according to any one of Items 1 to 3 above.
It comprises a first step of mixing a lithium compound with a nickel hydroxide and / or a water-soluble nickel salt in an aqueous solvent, and a second step of firing the mixture obtained by the first step in an oxidizing atmosphere. ,Production method.
Item 6. Item 4. The production method according to
Item 7. A positive electrode material for a lithium ion secondary battery containing the lithium nickel-based composite oxide according to any one of Items 1 to 3 above.
Item 8. A lithium ion secondary battery comprising the positive electrode material for a lithium ion secondary battery according to item 7 above.
本発明のリチウムニッケル系複合酸化物をリチウムイオン二次電池用の正極活物質として用いることにより、高容量を有し、かつ高いサイクル安定性を示すリチウムイオン二次電池を提供することが可能となる。 By using the lithium nickel-based composite oxide of the present invention as a positive electrode active material for a lithium ion secondary battery, it is possible to provide a lithium ion secondary battery having a high capacity and high cycle stability. Become.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
１．リチウムニッケル系複合酸化物
本発明は、リチウムニッケル系複合酸化物を包含する。本発明のリチウムニッケル系複合酸化物は、一般式（１）：
ＬｉｘＮｉＯ２＋δ （１）
［式中、ｘは０．８≦ｘ≦１．４を示し、δは－０．２０≦δ≦０．２０を示す。］
で表される化合物である。 1. 1. Lithium-Nickel-based Composite Oxide The present invention includes a lithium-nickel-based composite oxide. The lithium nickel-based composite oxide of the present invention has the general formula (1) :.
Li x NiO 2 + δ (1)
[In the equation, x indicates 0.8 ≦ x ≦ 1.4, and δ indicates −0.20 ≦ δ ≦ 0.20. ]
It is a compound represented by.
上記一般式（１）において、ｘは、ＬｉとＮｉとのモル比（Ｌｉ／Ｎｉ）に相当する。ｘが０．８未満であると容量の低下を招き、ｘが１．４を超えると結晶構造が電池特性の劣る単斜晶ＬｉＮｉＯ２－Ｌｉ２ＮｉＯ３系固溶体に変化することから、ｘは、０．８≦ｘ≦１．４である。また、サイクル特性の高い正極活物質とする観点からは、０．８≦ｘ≦１．３が好ましく、０．９≦ｘ≦１．３がより好ましい。In the above general formula (1), x corresponds to the molar ratio (Li / Ni) of Li and Ni. If x is less than 0.8, the capacity will decrease, and if x exceeds 1.4, the crystal structure will change to a monoclinic LiNiO 2 -Li 2 NiO 3 system solid solution with inferior battery characteristics. , 0.8 ≦ x ≦ 1.4. Further, from the viewpoint of using a positive electrode active material having high cycle characteristics, 0.8 ≦ x ≦ 1.3 is preferable, and 0.9 ≦ x ≦ 1.3 is more preferable.
上記一般式（１）において、δは、酸素量の不定比性に相当する。δは、－０．２０≦δ≦０．２０、好ましくは－０．１５≦δ≦０．１５、より好ましくは－０．１０≦δ≦０．１０である。 In the above general formula (1), δ corresponds to the non-stoichiometricity of the amount of oxygen. δ is −0.20 ≦ δ ≦ 0.20, preferably −0.15 ≦ δ ≦ 0.15, and more preferably −0.10 ≦ δ ≦ 0.10.
上記一般式（１）で表されるリチウムニッケル系複合酸化物としては、例えば、Ｌｉ１．１ＮｉＯ２、Ｌｉ１．１６ＮｉＯ２などが挙げられる。Examples of the lithium nickel-based composite oxide represented by the general formula (1) include Li 1.1 NiO 2 and Li 1.16 NiO 2 .
本発明のリチウムニッケル系複合酸化物は、空間群： The lithium nickel-based composite oxide of the present invention has a space group:
に帰属する六方晶層状岩塩型構造の結晶相を含む。本発明のリチウムニッケル系複合酸化物は、上記の六方晶層状岩塩型構造の結晶相を含んでいればよく、他の岩塩型構造の結晶相（例えば、立方晶岩塩型構造等）を含む混合相であってもよい。混合相である場合、六方晶層状岩塩型構造の結晶相の割合は、容量、サイクル特性、製造工程等の観点から、当該混合相全体を基準（１００重量％）として、５０～９０重量％が好ましい。また、本発明のリチウムニッケル系複合酸化物は、上記の六方晶層状岩塩型構造の結晶相のみからなるものであってもよい。 Includes the crystalline phase of the hexagonal layered rock salt structure attributed to. The lithium nickel-based composite oxide of the present invention may contain the above-mentioned crystal phase of the hexagonal layered rock salt type structure, and may contain a crystal phase of another rock salt type structure (for example, a cubic rock salt type structure). It may be a phase. In the case of a mixed phase, the ratio of the crystal phase of the hexagonal layered rock salt type structure is 50 to 90% by weight based on the entire mixed phase (100% by weight) from the viewpoint of capacity, cycle characteristics, manufacturing process, etc. preferable. Further, the lithium nickel-based composite oxide of the present invention may consist only of the crystal phase of the hexagonal layered rock salt type structure described above.
本発明のリチウムニッケル系複合酸化物は、容量、サイクル特性、製造工程等の観点から、Ｎｉ層（３ｂサイト）に存在する元素の総量を基準（１００％）として、Ｎｉ層内におけるＮｉイオンの占有率が９９．９％以下、特に８０．０～９９．０％であることが好ましい。 The lithium nickel-based composite oxide of the present invention contains Ni ions in the Ni layer based on the total amount of elements present in the Ni layer (3b site) from the viewpoints of capacity, cycle characteristics, manufacturing process, etc. The occupancy rate is preferably 99.9% or less, particularly preferably 80.0 to 99.0%.
本発明のリチウムニッケル系複合酸化物は、格子定数ａが２．８００Å以上２．８７０Å以下が好ましく、２．８３０Å以上２．８６５Å以下がより好ましく、２．８４０Å以上２．８６０Å以下が特に好ましい。格子定数ａが当該範囲にあることにより、サイクル特性に優れた正極活物質とすることができる。 The lithium nickel-based composite oxide of the present invention preferably has a lattice constant a of 2.800 Å or more and 2.870 Å or less, more preferably 2.830 Å or more and 2.865 Å or less, and particularly preferably 2.840 Å or more and 2.860 Å or less. When the lattice constant a is in the range, it is possible to obtain a positive electrode active material having excellent cycle characteristics.
本発明のリチウムニッケル系複合酸化物は、容量、サイクル特性、製造工程等の観点から、格子定数ｃが１４．１３０Å以上１４．１９０未満であり、１４．１３１Å以上１４．１８０以下が好ましく、１４．１３２Å以上１４．１７０Å以下がより好ましく、１４．１３３Å以上１４．１６０Å以下がさらに好ましく、１４．１３４Å以上１４．１５０Å以下が一層好ましく、１４．１３５Å以上１４．１４０Å以下が特に好ましい。 The lithium nickel-based composite oxide of the present invention has a lattice constant c of 14.130 Å or more and less than 14.190, preferably 14.131 Å or more and 14.180 or less, preferably 14 from the viewpoint of capacity, cycle characteristics, manufacturing process and the like. It is more preferably .132 Å or more and 14.170 Å or less, further preferably 14.133 Å or more and 14.160 Å or less, further preferably 14.134 Å or more and 14.150 Å or less, and particularly preferably 14.135 Å or more and 14.140 Å or less.
本発明のリチウムニッケル系複合酸化物は、容量、サイクル特性、製造工程等の観点から、格子定数ｃを格子定数ａで除した値（ｃ／ａ）が４．９４０以上４．９６０以下が好ましく、４．９４２以上４．９５０以下がより好ましい。 The lithium nickel-based composite oxide of the present invention preferably has a value (c / a) obtained by dividing the lattice constant c by the lattice constant a of 4.940 or more and 4.960 or less from the viewpoints of capacity, cycle characteristics, manufacturing process, and the like. More preferably, it is 4.942 or more and 4.950 or less.
本発明のリチウムニッケル系複合酸化物は、容量、サイクル特性、製造工程等の観点から、格子体積が１００．００Å３以上１００．５０Å３未満が好ましく、１００．０１Å３以上１００．４０Å３以下がより好ましく、１００．０２Å３以上１００．３０Å３以下がさらに好ましく、１００．０３Å３以上１００．２０Å３以下が一層好ましく、１００．０４Å３以上１００．１０Å３以下が特に好ましい。The lithium nickel-based composite oxide of the present invention preferably has a lattice volume of 100.00 Å 3 or more and less than 100.50 Å 3 from the viewpoint of capacity, cycle characteristics, manufacturing process, etc., preferably 100.01 Å 3 or more and 100.40 Å 3 or less. More preferably, 100.02 Å 3 or more and 100.30 Å 3 or less is further preferable, 100.03 Å 3 or more and 100.20 Å 3 or less is more preferable, and 100.04 Å 3 or more and 100.10 Å 3 or less is particularly preferable.
なお、上記した結晶構造、Ｎｉ層内におけるＮｉイオンの占有率、格子定数ａ及びｃ、並びに格子体積は、いずれもＣｕＫαを線源とし、回折角２θの測定範囲を１０°以上１２５°以下とする粉末Ｘ線回折測定を行い、当該測定結果を元にリートベルト解析を行うことにより決定又は算出したものである。 The crystal structure, the occupancy rate of Ni ions in the Ni layer, the lattice constants a and c, and the lattice volume all have CuKα as the radiation source, and the measurement range of the diffraction angle 2θ is 10 ° or more and 125 ° or less. It is determined or calculated by performing a powder X-ray diffraction measurement and performing a Rietveld analysis based on the measurement result.
２．リチウムニッケル系複合酸化物の製造方法
本発明は、さらに、上記したリチウムニッケル系複合酸化物の製造方法を包含する。本発明のリチウムニッケル系複合酸化物の製造方法は、水性溶媒中で、リチウム化合物と、水酸化ニッケル及び／又は水溶性ニッケル塩とを混合する工程（本明細書において「第１工程」と記載する場合がある。）、及び当該混合物を酸化性雰囲気下で焼成する工程（本明細書において「第２工程」と記載する場合がある。）を含む。 2. 2. Method for Producing Lithium-Nickel-based Composite Oxide The present invention further includes the above-mentioned method for producing a lithium-nickel-based composite oxide. The method for producing a lithium nickel-based composite oxide of the present invention is a step of mixing a lithium compound with a nickel hydroxide and / or a water-soluble nickel salt in an aqueous solvent (described as "first step" in the present specification. In some cases), and a step of firing the mixture in an oxidizing atmosphere (may be referred to as “second step” in the present specification).
第１工程において用いるリチウム化合物としては特に限定的ではなく、例えば、水酸化リチウム（水和物を含む）、炭酸リチウム、酢酸リチウム（水和物を含む）、硝酸リチウムなどが挙げられる。また、第１工程において用いるリチウム化合物は、仕込みニッケルのモル数に対して１．５倍以上２．５倍以下となるように添加することが好ましい。 The lithium compound used in the first step is not particularly limited, and examples thereof include lithium hydroxide (including hydrate), lithium carbonate, lithium acetate (including hydrate), lithium nitrate and the like. Further, the lithium compound used in the first step is preferably added so as to be 1.5 times or more and 2.5 times or less the number of moles of the charged nickel.
第１工程において用いる水酸化ニッケルとしては、市販のものを用いることができる。また、必要に応じて、水溶性ニッケル塩をアルカリで中和することにより得られるものを用いてもよい。この場合、あらかじめ水溶性ニッケル塩をアルカリで中和することにより得られた水酸化ニッケルを第１工程に使用することもできるし、水性溶媒中に水溶性ニッケル塩を投入して系中でアルカリで中和することで水酸化ニッケルを得ることもできる。水溶性ニッケル塩としては、例えば、硝酸塩、塩化物、硫酸塩、酢酸塩、及びその水和物などが挙げられる。また、水溶性ニッケル塩は１種単独で用いてもよいし、２種以上を混合して用いてもよい。 As the nickel hydroxide used in the first step, commercially available nickel hydroxide can be used. Further, if necessary, those obtained by neutralizing a water-soluble nickel salt with an alkali may be used. In this case, nickel hydroxide obtained by neutralizing the water-soluble nickel salt with an alkali in advance can be used in the first step, or the water-soluble nickel salt is put into an aqueous solvent and alkaline in the system. Nickel hydroxide can also be obtained by neutralizing with. Examples of the water-soluble nickel salt include nitrates, chlorides, sulfates, acetates, and hydrates thereof. Further, the water-soluble nickel salt may be used alone or in combination of two or more.
水溶性ニッケル塩を中和する際に用いるアルカリとしては特に限定的ではなく、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、アンモニアなどを用いることができる。アルカリの濃度は、アルカリに対して水溶性ニッケル塩を滴下していく中和工程の間中、ｐＨ１１以上を維持できる濃度であればよい。また、中和工程時の温度は－１０℃以上５０℃以下とすることが好ましい。中和温度を低下させることにより水酸化ニッケルの核生成速度が速くなり、より微細な反応性の高い水酸化ニッケルを得ることができる。特に反応温度を０℃以下に保持するために、アルカリ水溶液にエタノールなどの不凍液を加えても良い。このように、低温で反応させる場合、アルカリとしては水酸化リチウムを用いることが好ましい。水酸化リチウム不純物として他のアルカリイオンを除去する必要がないうえに、残存する水酸化リチウムは上記したリチウム化合物として使用することもできるという工程上のメリットがある。中和工程時にアルカリ溶液に水溶性ニッケル塩を加えるには、均一な水酸化ニッケルを得るために滴下工程により数時間かけて徐々に行うことが好ましい。また、必要に応じて滴下終了後、沈殿を熟成するために沈殿を室温にて空気を吹き込みながら数時間以上撹拌してもよい。さらに、必要に応じて、沈殿を調製した後、残留アルカリを除去するために、沈殿を蒸留水で水洗後、濾過してもよい。 The alkali used for neutralizing the water-soluble nickel salt is not particularly limited, and for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia and the like can be used. The concentration of the alkali may be any concentration that can maintain pH 11 or higher during the neutralization step of dropping the water-soluble nickel salt with respect to the alkali. The temperature during the neutralization step is preferably −10 ° C. or higher and 50 ° C. or lower. By lowering the neutralization temperature, the nucleation rate of nickel hydroxide becomes faster, and finer and more reactive nickel hydroxide can be obtained. In particular, in order to keep the reaction temperature below 0 ° C., an antifreeze solution such as ethanol may be added to the alkaline aqueous solution. As described above, when the reaction is carried out at a low temperature, it is preferable to use lithium hydroxide as the alkali. It is not necessary to remove other alkaline ions as lithium hydroxide impurities, and the remaining lithium hydroxide can be used as the above-mentioned lithium compound, which has a merit in the process. In order to add the water-soluble nickel salt to the alkaline solution during the neutralization step, it is preferable to gradually carry out by a dropping step over several hours in order to obtain uniform nickel hydroxide. Further, if necessary, after the completion of the dropping, the precipitate may be stirred at room temperature for several hours or more while blowing air to mature the precipitate. Further, if necessary, after preparing the precipitate, the precipitate may be washed with distilled water and then filtered in order to remove the residual alkali.
このような第１工程の具体的な方法としては、特に制限されないが、本発明のリチウムニッケル系複合酸化物の得やすさと製造工程の容易さの観点から、リチウム化合物を含む水溶液に水酸化ニッケル及び／又は水溶性ニッケル塩を添加する工程とすることが好ましい。この場合、第１工程において用いるリチウム化合物を含む水溶液は、アルカリ性であることが好ましい。アルカリ源としては特に限定的ではなく、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、アンモニアなどを用いることができる。また、水酸化リチウムは、アルカリ源としてだけではなく、リチウム化合物としても作用するため好ましい。 The specific method of such a first step is not particularly limited, but from the viewpoint of the ease of obtaining the lithium nickel-based composite oxide of the present invention and the ease of the manufacturing process, nickel hydroxide is added to the aqueous solution containing the lithium compound. And / or the step of adding a water-soluble nickel salt is preferable. In this case, the aqueous solution containing the lithium compound used in the first step is preferably alkaline. The alkali source is not particularly limited, and for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia and the like can be used. Further, lithium hydroxide is preferable because it acts not only as an alkali source but also as a lithium compound.
また、本発明のリチウムニッケル系複合酸化物の製造方法は、上記した第１工程の後、後述する第２工程に供する前に、必要に応じて、混合物を乾燥する工程を含むことが好ましい。乾燥方法としては特に限定的ではなく常法に従って行うことができる。例えば、第１工程で得られた混合物をシャーレ等の容器に移し、５０℃以上に保温した乾燥機に入れて数時間乾燥を行う方法などが挙げられる。当該乾燥工程により、第１工程で得られた混合物の乾燥粉末を調製することができる。また、乾燥後、第２工程に供する前に、必要に応じて得られた乾燥粉末を粉砕してもよい。 Further, the method for producing a lithium nickel-based composite oxide of the present invention preferably includes, if necessary, a step of drying the mixture after the above-mentioned first step and before subjecting it to the second step described later. The drying method is not particularly limited and can be carried out according to a conventional method. For example, a method of transferring the mixture obtained in the first step to a container such as a petri dish, placing it in a dryer kept at 50 ° C. or higher, and drying it for several hours can be mentioned. By the drying step, a dry powder of the mixture obtained in the first step can be prepared. Further, after drying, the obtained dry powder may be crushed, if necessary, before being subjected to the second step.
第２工程では、第１工程で得られた混合物を酸化性雰囲気下で焼成する。酸化性雰囲気としては特に限定的ではなく、例えば、大気中雰囲気、酸素気流中などが挙げられる。焼成温度としては、６９０℃を超えるとサイクル特性が劣化するおそれがあるため、６９０℃以下の温度であり、好ましくは６００℃以上６９０℃以下、より好ましくは６２０℃以上６８０℃以下である。また、焼成時間としては特に限定的ではなく、例えば、１時間～３０時間程度とすることができる。なお、この焼成は、過度の焼成をしないことでサイクル特性をより向上させる観点からは、複数回行わず、１回だけ行うことが好ましい。 In the second step, the mixture obtained in the first step is calcined in an oxidizing atmosphere. The oxidizing atmosphere is not particularly limited, and examples thereof include an atmospheric atmosphere and an oxygen air stream. The firing temperature is 690 ° C. or lower, preferably 600 ° C. or higher and 690 ° C. or lower, and more preferably 620 ° C. or higher and 680 ° C. or lower, because the cycle characteristics may deteriorate if the firing temperature exceeds 690 ° C. The firing time is not particularly limited, and may be, for example, about 1 hour to 30 hours. From the viewpoint of further improving the cycle characteristics by preventing excessive firing, it is preferable to perform this firing only once, not a plurality of times.
また、本発明のリチウムニッケル系複合酸化物の製造方法は、上記した第２工程により得られた焼成物を冷却する工程を含むことが好ましい。焼成物の冷却方法としては特に限定的ではなく常法に従って行うことができ、例えば、焼成後、炉内で室温付近まで放置する方法などが挙げられる。 Further, the method for producing a lithium nickel-based composite oxide of the present invention preferably includes a step of cooling the fired product obtained by the above-mentioned second step. The method for cooling the fired product is not particularly limited and can be carried out according to a conventional method. For example, a method of leaving the fired product in a furnace to around room temperature after firing may be mentioned.
さらに、本発明のリチウムニッケル系複合酸化物の製造方法は、必要に応じて、上記した冷却工程を経た後、得られた焼成物を粉砕する工程、洗浄する工程、濾過する工程、及び乾燥する工程の少なくとも１つの工程を含むことが好ましい。これらの工程の具体的な方法としては特に限定的ではなく、常法に従って行うことができる。 Further, in the method for producing a lithium nickel-based composite oxide of the present invention, if necessary, after the above-mentioned cooling step, the obtained fired product is crushed, washed, filtered, and dried. It is preferable to include at least one step of the step. The specific method of these steps is not particularly limited, and can be performed according to a conventional method.
３．リチウムイオン二次電池用正極材料及びリチウムイオン二次電池
上記した本発明のリチウムニッケル系複合酸化物は、リチウムイオン二次電池用正極材料として用いることができる。さらに、当該リチウムイオン二次電池用正極材料、負極、電解質（固体電解質を含む）、及びセパレータと組み合わせることにより、高容量かつサイクル特性に優れたリチウムイオン二次電池（非水系リチウムイオン二次電池及び全固体リチウムイオン二次電池）とすることができる。負極としては特に限定的ではなく、例えば、金属リチウム、黒鉛、Ｓｉ－ＳｉＯ系負極、ＬＴＯ系負極などが挙げられる。電解質としては特に限定的ではなく、ＬｉＰＦ６を支持塩とし、炭酸エチル（ＥＣ）や炭酸ジメチル（ＤＭＣ）などの各種溶媒に溶解させた有機電解液、Ｌｉ２Ｓ－Ｐ２Ｓ５、Ｌｉ２Ｓ－ＧｅＳ２－Ｐ２Ｓ５、Ｌｉ２Ｓ－ＳｉＳ２－Ｌｉ３ＰＯ４などの無機硫化物系固体電解質、リチウムイオン導電性を有する高分子ポリマーなどが挙げられる。セパレータとしては特に限定的ではなく、ポリエチレン、ポリプロピレンなどが挙げられる。 3. 3. Positive Material for Lithium Ion Secondary Battery and Lithium Ion Secondary Battery The lithium nickel-based composite oxide of the present invention described above can be used as the positive electrode material for lithium ion secondary battery. Furthermore, by combining with the positive electrode material, negative electrode, electrolyte (including solid electrolyte), and separator for the lithium ion secondary battery, the lithium ion secondary battery (non-aqueous lithium ion secondary battery) with high capacity and excellent cycle characteristics And an all-solid-state lithium-ion secondary battery). The negative electrode is not particularly limited, and examples thereof include metallic lithium, graphite, Si—SiO-based negative electrode, and LTO-based negative electrode. The electrolyte is not particularly limited, and an organic electrolytic solution in which LiPF 6 is used as a supporting salt and dissolved in various solvents such as ethyl carbonate (EC) and dimethyl carbonate (DMC), Li 2 SP 2 S 5 , Li 2 Examples thereof include inorganic sulfide-based solid electrolytes such as S-GeS 2 -P 2 S 5 , Li 2 S-SiS 2 -Li 3 PO 4 , and high-molecular polymers having lithium ion conductivity. The separator is not particularly limited, and examples thereof include polyethylene and polypropylene.
以下、実施例を挙げて本発明をさらに詳細に説明するが、本発明は下記の例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
［実施例１］
試料の調製
水酸化リチウム１水和物２０．９８ｇ（０．５０ｍｏｌ）を２００ｍｌの蒸留水に加え完全に溶解させた。当該水酸化リチウム溶液に水酸化ニッケル２３．１８ｇ（０．２５ｍｏｌ）を加えて撹拌して分散させた。得られた混合物をポリテトラフルオロエチレン製シャーレに移し、当該シャーレを１００℃に保たれた乾燥機に入れ、３時間かけて乾燥を行った。得られた乾燥粉末を粉砕混合し、電気炉にて酸素気流中１時間かけて６５０℃に昇温し、２０時間焼成を行い、その後、炉内で室温付近まで冷却して焼成物を得た。得られた焼成物を粉砕後、蒸留水を用いて水洗処理を行った後、濾過し、１００℃で乾燥することにより生成物を得た。[Example 1]
Sample preparation
20.98 g (0.50 mol) of lithium hydroxide monohydrate was added to 200 ml of distilled water to completely dissolve it. 23.18 g (0.25 mol) of nickel hydroxide was added to the lithium hydroxide solution, and the mixture was stirred and dispersed. The obtained mixture was transferred to a petri dish made of polytetrafluoroethylene, and the petri dish was placed in a dryer kept at 100 ° C. and dried for 3 hours. The obtained dry powder was pulverized and mixed, heated to 650 ° C. in an oxygen stream for 1 hour in an electric furnace, calcined for 20 hours, and then cooled to near room temperature in the furnace to obtain a calcined product. .. The obtained calcined product was pulverized, washed with distilled water, filtered, and dried at 100 ° C. to obtain a product.
Ｘ線回折による評価
上記で得られた生成物の実測（＋）及び計算（実線）Ｘ線回折パターンを図１に示す。また、リートベルト解析により、得られた生成物が層状岩塩型構造を有する六方晶ＬｉＮｉＯ２単相であること、格子定数ａが２．８５８５６（７）Å、格子定数ｃが１４．１３８３（３）Å、格子体積が１００．０５１（４）Å３、ｃ／ａ値が４．９４６、Ｎｉ層内のＮｉイオン占有率が９０．４（２）％、Ｌｉ層内のＮｉイオン占有率が１．２７（７）％であることが分かった。 Evaluation by X-ray Diffraction The measured (+) and calculated (solid) X-ray diffraction patterns of the products obtained above are shown in FIG. In addition, the product obtained by Rietveld analysis is a hexagonal LiNiO 2 single phase having a layered rock salt structure, the lattice constant a is 2.58556 (7) Å, and the lattice constant c is 14.1383 (3). ) Å, lattice volume is 100.051 (4) Å 3 , c / a value is 4.946, Ni ion occupancy in Ni layer is 90.4 (2)%, Ni ion occupancy in Li layer is It was found to be 1.27 (7)%.
化学分析
ＩＣＰ発光分析により上記で得られた生成物の化学組成を求めたところ、Ｌｉ／Ｎｉ比が１．１６であることが分かった。 Chemical analysis When the chemical composition of the product obtained above was determined by ICP emission analysis, it was found that the Li / Ni ratio was 1.16.
充放電特性評価
上記で得られた生成物５ｍｇをアセチレンブラック５ｍｇと混合した後、ポリテトラフルオロエチレン０．５ｍｇを用いて正極合材を作製し、当該正極合材をアルミニウムメッシュに圧着して正極とした。次いで、当該正極、負極として金属リチウム、電解液として１Ｍ ＬｉＰＦ６／ＥＣ＋ＤＭＣ系、及びセパレータを用いてコイン型電池を作製し、充放電試験を行った。充放電試験は充電開始で、電位範囲：２．２～４．８Ｖ、正極活物質あたりの電流密度：４０ｍＡ／ｇ、試験温度：３０℃の条件で５０サイクルまで行った。結果を図２に示す。また、負極として黒鉛を用い、電位範囲を２．０～４．６Ｖとしたこと以外は上記と同様にして充放電試験を行った。結果を図３に示す。 Evaluation of charge / discharge characteristics After mixing 5 mg of the product obtained above with 5 mg of acetylene black, a positive electrode mixture was prepared using 0.5 mg of polytetrafluoroethylene, and the positive electrode mixture was crimped onto an aluminum mesh to form a positive electrode. And said. Next, a coin-type battery was prepared using the positive electrode, metallic lithium as the negative electrode, 1M LiPF 6 / EC + DMC system as the electrolytic solution, and a separator, and a charge / discharge test was performed. The charge / discharge test was carried out at the start of charging under the conditions of a potential range of 2.2 to 4.8 V, a current density of 40 mA / g per positive electrode active material, and a test temperature of 30 ° C. up to 50 cycles. The results are shown in FIG. Further, a charge / discharge test was carried out in the same manner as above except that graphite was used as the negative electrode and the potential range was 2.0 to 4.6 V. The results are shown in FIG.
また、上記で得られた生成物、ケッチェンブラック、ポリテトラフルオロエチレンを８４：８：８の重量比で混合し、段階充電法（４０ｍＡｈ／ｇ充電からスタートし、放電後、充電容量を４０ｍＡｈ／ｇずつ上昇させて２００ｍＡｈ／ｇまで充電容量を伸ばしサイクルさせ、次に４．６Ｖまで充電後２．０Ｖまで放電させる方法）にて活性化後、２．０～４．６Ｖで２０サイクル充放電させた。結果を図４に示す。初期放電容量は２２２ｍＡｈ／ｇに達し、２０サイクル後の放電容量は８９％を維持していた。このことから、正極材料中の活物質量を８４％にまで上げても良好な充放電特性を示すことがわかった。 Further, the products obtained above, Ketjen black, and polytetrafluoroethylene are mixed at a weight ratio of 84: 8: 8, and a stepwise charging method (starting from 40 mAh / g charging, and after discharging, the charging capacity is 40 mAh. Increase by / g in increments of 200mAh / g to extend the charge capacity and cycle, then charge to 4.6V and then discharge to 2.0V), and then charge for 20 cycles at 2.0 to 4.6V. It was discharged. The results are shown in FIG. The initial discharge capacity reached 222 mAh / g, and the discharge capacity after 20 cycles was maintained at 89%. From this, it was found that even if the amount of active material in the positive electrode material was increased to 84%, good charge / discharge characteristics were exhibited.
［比較例１］
試料の調製
水酸化リチウム１水和物１０．７０ｇ（０．２５５ｍｏｌ）を２００ｍｌの蒸留水に加え完全に溶解させた。当該水酸化リチウム溶液に水酸化ニッケル２３．１８ｇ（０．２５ｍｏｌ）を加えて撹拌して分散させた。得られた混合物をポリテトラフルオロエチレン製シャーレに移し、当該シャーレを１００℃に保たれた乾燥機に入れ、３時間かけて乾燥を行った。得られた乾燥粉末を粉砕混合し、電気炉にて酸素気流中１時間かけて７００℃に昇温し、２０時間焼成を行い、その後、炉内で室温付近まで冷却して焼成物を得た。得られた焼成物を粉砕後、再度、電気炉にて酸素気流中１時間かけて７００℃に昇温し、２０時間焼成を行い、その後、炉内で室温付近まで冷却して焼成物を得た。得られた焼成物を粉砕後、蒸留水を用いて水洗処理を行った後、濾過し、１００℃で乾燥することにより生成物を得た。[Comparative Example 1]
Sample preparation
10.70 g (0.255 mol) of lithium hydroxide monohydrate was added to 200 ml of distilled water to completely dissolve it. 23.18 g (0.25 mol) of nickel hydroxide was added to the lithium hydroxide solution, and the mixture was stirred and dispersed. The obtained mixture was transferred to a petri dish made of polytetrafluoroethylene, and the petri dish was placed in a dryer kept at 100 ° C. and dried for 3 hours. The obtained dry powder was pulverized and mixed, heated to 700 ° C. in an oxygen stream for 1 hour in an electric furnace, calcined for 20 hours, and then cooled to near room temperature in the furnace to obtain a calcined product. .. After crushing the obtained calcined product, the temperature is raised to 700 ° C. in an oxygen stream for 1 hour again in an electric furnace, and the calcined product is fired for 20 hours, and then cooled to near room temperature in the furnace to obtain a calcined product. rice field. The obtained calcined product was pulverized, washed with distilled water, filtered, and dried at 100 ° C. to obtain a product.
Ｘ線回折による評価
上記で得られた生成物の実測（＋）及び計算（実線）Ｘ線回折パターンを図５に示す。また、リートベルト解析により、得られた生成物が層状岩塩型構造を有する六方晶ＬｉＮｉＯ２単相であること、格子定数ａが２．８７５８９（３）Å、格子定数ｃが１４．１９１５０（１３）Å、格子体積が１００．６４８９（１８）Å３、ｃ／ａ値が４．９３５、Ｎｉ層内のＮｉイオン占有率が１００％、Ｌｉ層内のＮｉイオン占有率が０．５６（５）％であることが分かった。 Evaluation by X-ray Diffraction The measured (+) and calculated (solid) X-ray diffraction patterns of the products obtained above are shown in FIG. In addition, the product obtained by Rietveld analysis is a hexagonal LiNiO 2 single phase having a layered rock salt structure, the lattice constant a is 2.87589 (3) Å, and the lattice constant c is 14.19150 (13). ) Å, lattice volume is 100.6489 (18) Å 3 , c / a value is 4.935, Ni ion occupancy in Ni layer is 100%, Ni ion occupancy in Li layer is 0.56 (5). )% Turned out.
化学分析
ＩＣＰ発光分析により上記で得られた生成物の化学組成を求めたところ、Ｌｉ／Ｎｉ比が１．０２であることが分かった。 Chemical analysis When the chemical composition of the product obtained above was determined by ICP emission analysis, it was found that the Li / Ni ratio was 1.02.
充放電特性評価
上記で得られた生成物５ｍｇをアセチレンブラック５ｍｇと混合した後、ポリテトラフルオロエチレン０．５ｍｇを用いて正極合材を作製し、当該正極合材をアルミニウムメッシュに圧着して正極とした。次いで、当該正極、負極として金属リチウム、電解液として１Ｍ ＬｉＰＦ６／ＥＣ＋ＤＭＣ系、及びセパレータを用いてコイン型電池を作製し、充放電試験を行った。充放電試験は充電開始で、電位範囲：２．２～４．８Ｖ、正極活物質あたりの電流密度：４０ｍＡ／ｇ、試験温度：３０℃の条件で５０サイクルまで行った。結果を図６に示す。また、負極として黒鉛を用い、電位範囲を２．０～４．６Ｖとしたこと以外は上記と同様にして充放電試験を行った。結果を図７に示す。 Evaluation of charge / discharge characteristics After mixing 5 mg of the product obtained above with 5 mg of acetylene black, a positive electrode mixture was prepared using 0.5 mg of polytetrafluoroethylene, and the positive electrode mixture was crimped onto an aluminum mesh to form a positive electrode. And said. Next, a coin-type battery was prepared using the positive electrode, metallic lithium as the negative electrode, 1M LiPF 6 / EC + DMC system as the electrolytic solution, and a separator, and a charge / discharge test was performed. The charge / discharge test was carried out at the start of charging under the conditions of a potential range of 2.2 to 4.8 V, a current density of 40 mA / g per positive electrode active material, and a test temperature of 30 ° C. up to 50 cycles. The results are shown in FIG. Further, a charge / discharge test was carried out in the same manner as above except that graphite was used as the negative electrode and the potential range was 2.0 to 4.6 V. The results are shown in FIG.
［結果及び考察］
以上の実施例１及び比較例１の試料のＸ線回折による評価結果及び化学分析結果を下記表１に、充放電特性評価の結果を下記表２に示す。[Results and discussion]
The evaluation results and chemical analysis results of the samples of Example 1 and Comparative Example 1 by X-ray diffraction are shown in Table 1 below, and the results of charge / discharge characteristic evaluation are shown in Table 2 below.
以上の結果から、実施例１の試料は、比較例１の試料と比較して、負極が金属リチウムの場合及び黒鉛の場合のいずれにおいても、初期充放電容量、初期放電平均電圧、及び初期放電エネルギー密度はやや劣るもののリチウムイオン二次電池用正極材料として十分使用可能な水準であり、初期充放電効率は同程度であり、５０サイクル後の放電容量及び５０サイクル後の放電容量維持率が優れていることが分かった。
From the above results, the sample of Example 1 has an initial charge / discharge capacity, an initial discharge average voltage, and an initial discharge regardless of whether the negative electrode is metallic lithium or graphite as compared with the sample of Comparative Example 1. Although the energy density is slightly inferior, it is at a level that can be sufficiently used as a positive electrode material for lithium ion secondary batteries, the initial charge / discharge efficiency is about the same, and the discharge capacity after 50 cycles and the discharge capacity retention rate after 50 cycles are excellent. It turned out that.
Claims (7)
ＬｉｘＮｉＯ２＋δ （１）
［式中、ｘは０．８≦ｘ≦１．３を示し、δは－０．２０≦δ≦０．２０を示す。］
で表されるリチウムニッケル系複合酸化物であって、
六方晶層状岩塩型構造の結晶相を含み、
Ｎｉ層内におけるＮｉイオンの占有率が９９．９％以下であり、格子定数ａが２．８００Å以上２．８７０Å以下であり、格子定数ｃが１４．１３０Å以上１４．１９０Å未満であり、格子定数ｃを格子定数ａで除した値（ｃ／ａ）が４．９４０以上４．９６０以下であり、且つ、格子体積が１００．００Å３以上１００．５０Å３未満である、リチウムニッケル系複合酸化物。 General formula (1):
Li x NiO 2 + δ (1)
[In the equation, x indicates 0.8 ≦ x ≦ 1.3, and δ indicates −0.20 ≦ δ ≦ 0.20. ]
It is a lithium nickel-based composite oxide represented by
Containing a crystalline phase of hexagonal layered rock salt type structure,
The occupancy of Ni ions in the Ni layer is 99.9% or less, the lattice constant a is 2.800 Å or more and 2.870 Å or less, the lattice constant c is 14.130 Å or more and less than 14.190 Å , and the lattice . Lithium-nickel-based composite oxidation in which the value (c / a) obtained by dividing the constant c by the lattice constant a is 4.940 or more and 4.960 or less, and the lattice volume is 100.00 Å 3 or more and less than 100.50 Å 3 . thing.
水性溶媒中で、リチウム化合物と、水酸化ニッケル及び／又は水溶性ニッケル塩とを混合する第１工程、及び
前記第１工程により得られた混合物を酸化性雰囲気下で焼成する第２工程
を含む、製造方法。 The method for producing a lithium nickel-based composite oxide according to claim 1 or 2.
It comprises a first step of mixing a lithium compound with a nickel hydroxide and / or a water-soluble nickel salt in an aqueous solvent, and a second step of firing the mixture obtained by the first step in an oxidizing atmosphere. ,Production method.
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