JP6136869B2 - Method of treating lithium nickel-containing composite oxide, positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery having the same - Google Patents
Method of treating lithium nickel-containing composite oxide, positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery having the same Download PDFInfo
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- JP6136869B2 JP6136869B2 JP2013235135A JP2013235135A JP6136869B2 JP 6136869 B2 JP6136869 B2 JP 6136869B2 JP 2013235135 A JP2013235135 A JP 2013235135A JP 2013235135 A JP2013235135 A JP 2013235135A JP 6136869 B2 JP6136869 B2 JP 6136869B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、リチウムニッケル含有複合酸化物の処理方法及びリチウムイオン二次電池用正極活物質およびそれを有するリチウムイオン二次電池に関するものである。 The present invention relates to a method for treating a lithium nickel-containing composite oxide, a positive electrode active material for a lithium ion secondary battery, and a lithium ion secondary battery having the same.
近年、携帯電話やノート型パソコンなどの携帯機器の普及に伴い、高いエネルギー密度を有し、小型、軽量で高い容量を持つ二次電池の開発が強く望まれている。現在、高容量二次電池としては、正極材料としてコバルト酸リチウム（ＬｉＣｏＯ２）、負極材料として炭素系材料を用いたリチウムイオン二次電池が商品化されている。 In recent years, with the widespread use of mobile devices such as mobile phones and notebook computers, development of secondary batteries having high energy density, small size, light weight and high capacity is strongly desired. Currently, lithium ion secondary batteries using lithium cobalt oxide (LiCoO 2 ) as a positive electrode material and a carbon-based material as a negative electrode material are commercialized as high capacity secondary batteries.
正極活物質として、コバルトよりも安価なニッケルを用いたリチウムニッケル複合酸化物が検討されている。しかしながら、このリチウムニッケル複合酸化物は、化学量論性に優れたものが得られにくく、合成が困難であるとされている。リチウムニッケル複合酸化物は、Ｎｉ３＋が高温では不安定であるため、非化学量論組成：ＬｉｘＮｉ１−ｘＯ２（０＜ｘ＜１）を有する化合物になりやすいからである。 As a positive electrode active material, a lithium nickel composite oxide using nickel, which is cheaper than cobalt, has been studied. However, this lithium nickel composite oxide is said to be difficult to be synthesized because it is difficult to obtain a lithium oxide having a good stoichiometry. Lithium nickel composite oxide, since Ni 3+ is unstable at high temperatures, non-stoichiometry: because prone to Li x Ni 1-x O 2 (0 <x <1) compound having a.
そのため、できるだけ化学量論比に近いリチウムニッケル複合酸化物を製造するために検討が行われている。例えば特許文献１では、Ｘ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率が９０％以上であるリチウム複合酸化物を製造する方法を開示している。特許文献１に記載の方法では、リチウム複合酸化物前駆体原料を昇温速度１℃／ｍｉｎ以上で焼成を行い、冷却することによってリチウム複合酸化物を得ている。 Therefore, studies have been made to produce a lithium nickel composite oxide as close to the stoichiometric ratio as possible. For example, Patent Document 1 discloses a method for producing a lithium composite oxide having a lithium content of 90% or more in the 3a site by a Rietveld analysis method using X-ray diffraction. In the method described in Patent Document 1, a lithium composite oxide precursor material is baked at a temperature rising rate of 1 ° C./min or more and cooled to obtain a lithium composite oxide.
また特許文献２では、やはり原料混合物を焼成することによってＸ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率が９８％以上であるリチウム複合酸化物を製造する方法を開示している。 Patent Document 2 discloses a method for producing a lithium composite oxide having a lithium content of 98% or more in the 3a site by the Rietveld analysis method by X-ray diffraction by firing the raw material mixture.
このようにリチウム複合酸化物の原料や製造方法を工夫することによって化学量論比の高いリチウム複合酸化物を製造しているが、すでに製造されたリチウム複合酸化物に何らかの処理をすることによって化学量論比を高める検討は行われていない。 In this way, lithium composite oxides with a high stoichiometric ratio are manufactured by devising the raw materials and manufacturing methods for lithium composite oxides, but chemicals can be obtained by treating the already manufactured lithium composite oxides. There is no investigation to increase the stoichiometric ratio.
本発明はこのような事情に鑑みて為されたものであり、Ｘ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率を高めることができるリチウムニッケル含有複合酸化物の処理方法を提供することを目的とする。 This invention is made | formed in view of such a situation, and provides the processing method of lithium nickel containing complex oxide which can raise the lithium content to occupy 3a site by the Rietveld analysis method by X-ray diffraction. For the purpose.
本発明者等が鋭意検討した結果、層状岩塩構造を有するリチウムニッケル含有複合酸化物に下記の処理を行うことによりＸ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率を高めることができることを見いだした。 As a result of intensive studies by the present inventors, it is possible to increase the lithium content in the 3a site by the Rietveld analysis method by X-ray diffraction by performing the following treatment on the lithium nickel-containing composite oxide having a layered rock salt structure. I found.
すなわち、本発明のリチウムニッケル含有複合酸化物の処理方法は、層状岩塩構造を有するリチウムニッケル含有複合酸化物をＺｒＯ（ＮＯ３）２・２Ｈ２Ｏと（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを含む第１水溶液またはＶＯＳＯ４と（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを含む第２水溶液で処理する第一工程と、第一工程後のリチウムニッケル含有複合酸化物を４００℃以上７００℃以下の温度で焼成する第二工程と、を有することを特徴とする。 That is, in the method for treating a lithium nickel-containing composite oxide of the present invention, a lithium nickel-containing composite oxide having a layered rock salt structure is converted into ZrO (NO 3 ) 2 .2H 2 O and (NH 4 ) 2 HPO 4 .6H 2 O. A first step of treating with a first aqueous solution containing VOSO 4 and a second aqueous solution containing (NH 4 ) 2 HPO 4 .6H 2 O, and a lithium nickel-containing composite oxide after the first step at 400 ° C. or higher And a second step of firing at a temperature of 700 ° C. or lower.
リチウムニッケル含有複合酸化物は、一般式：ＬｉａＣｏｐＮｉｑＭｎｒＤｓＯｘ（Ｄは、Ａｌ、Ｍｇ、Ｔｉ、Ｓｎ、Ｚｎ、Ｗ、Ｚｒ、Ｍｏ、Ｆｅ及びＮａから選ばれる少なくとも１つであり、ｐ＋ｑ＋ｒ＋ｓ＝１、０≦ｐ＜１、０＜ｑ＜１、０≦ｒ＜１、０≦ｓ＜１、０．８≦ａ＜２．０、−０．２≦ｘ−（ａ＋ｐ＋ｑ＋ｒ＋ｓ）≦０．２）で表される化合物であることが好ましい。 Lithium-nickel-containing composite oxide is represented by the general formula: Li a Co p Ni q Mn r D s O x (D at least to, Al, Mg, Ti, Sn , Zn, W, Zr, Mo, selected from Fe and Na P + q + r + s = 1, 0 ≦ p <1, 0 <q <1, 0 ≦ r <1, 0 ≦ s <1, 0.8 ≦ a <2.0, −0.2 ≦ x− A compound represented by (a + p + q + r + s) ≦ 0.2) is preferable.
リチウムニッケル含有複合酸化物は、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉ０．６Ｃｏ０．２Ｍｎ０．２Ｏ２及びＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２から選択される少なくとも一つであることが好ましい。 Lithium nickel-containing composite oxides are LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 and LiNi 0.5 Co 0.2 Mn 0.3 It is preferably at least one selected from O 2 .
本発明のリチウムイオン二次電池用正極活物質は、上記リチウムニッケル含有複合酸化物の処理方法によって処理されたことを特徴とする。 The positive electrode active material for a lithium ion secondary battery of the present invention is characterized by being treated by the method for treating a lithium nickel-containing composite oxide.
本発明のリチウムイオン二次電池は上記のリチウムイオン二次電池用正極活物質を有することを特徴とする。 The lithium ion secondary battery of the present invention is characterized by having the above-described positive electrode active material for a lithium ion secondary battery.
本発明のリチウムニッケル含有複合酸化物の処理方法は、既存の層状岩塩構造を有するリチウムニッケル含有複合酸化物に対して、第一工程及び第二工程を施すことにより、Ｘ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率を高めることができる。 The method for treating a lithium nickel-containing composite oxide according to the present invention is a Rietveld analysis by X-ray diffraction by applying a first step and a second step to a lithium nickel containing composite oxide having an existing layered rock salt structure. According to the method, the lithium content in the 3a site can be increased.
またその処理方法で処理されたリチウムニッケル含有複合酸化物は化学量論比に近いリチウムニッケル複合酸化物となるため、結晶構造が安定し、リチウムイオンが出入りしやすくなる。そのため処理方法で処理されたリチウムニッケル含有複合酸化物を正極活物質として用いるとリチウムイオン二次電池の放電容量が未処理のリチウムニッケル含有複合酸化物からなる正極活物質を用いたものより向上する。 Further, since the lithium nickel-containing composite oxide treated by the treatment method becomes a lithium nickel composite oxide close to the stoichiometric ratio, the crystal structure is stabilized and lithium ions easily enter and exit. Therefore, when the lithium nickel-containing composite oxide treated by the treatment method is used as the positive electrode active material, the discharge capacity of the lithium ion secondary battery is improved from that using the positive electrode active material comprising the untreated lithium nickel-containing composite oxide. .
＜リチウムニッケル含有複合酸化物の処理方法＞
本発明のリチウムニッケル含有複合酸化物の処理方法は、第一工程と、第二工程とを有する。
<Processing method for lithium nickel-containing composite oxide>
The processing method of lithium nickel containing complex oxide of this invention has a 1st process and a 2nd process.
第一工程では、層状岩塩構造を有するリチウムニッケル含有複合酸化物をＺｒＯ（ＮＯ３）２・２Ｈ２Ｏと（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを含む第１水溶液またはＶＯＳＯ４と（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを含む第２水溶液で処理する。 In the first step, a lithium nickel-containing composite oxide having a layered rock salt structure is converted into a first aqueous solution or VOSO 4 containing ZrO (NO 3 ) 2 .2H 2 O and (NH 4 ) 2 HPO 4 .6H 2 O ( Treat with a second aqueous solution containing NH 4 ) 2 HPO 4 .6H 2 O.
層状岩塩構造とは、α―ＮａＦｅＯ２型の六方晶系の層状岩塩構造である。六方晶系の化合物の場合には、結晶中に原子が占める特定の場所のうち結晶学的に等価な原子位置を一まとめにしたものであるサイトには、３ａサイト、３ｂサイト、６ｃサイトの三種類がある。完全な化学量論組成の場合には、ＬｉＮｉＯ２の３ａサイトはＬｉ、３ｂサイトはＮｉ、６ｃサイトはＯがそれぞれ１００％の席占有率（含有率）を示す。３ａサイトのＬｉイオンの含有率が９０％以上であるようなリチウムニッケル複合酸化物は化学量論性に優れていると言える。通常、層状岩塩構造を有するリチウムニッケル複合酸化物はＬｉ層に遷移金属、特にＮｉが不規則配列し、遷移金属層にＬｉが不規則配列する。不規則配列が少ない方が、結晶構造が安定する。 The layered rock salt structure is an α-NaFeO 2 type hexagonal layered rock salt structure. In the case of a hexagonal compound, a site that is a group of crystallographically equivalent atomic positions out of specific locations occupied by atoms in the crystal includes 3a site, 3b site, and 6c site. There are three types. In the case of a perfect stoichiometric composition, the LiNiO 2 3a site has Li, the 3b site Ni, and the 6c site O has 100% seat occupancy (content). It can be said that the lithium nickel composite oxide in which the content of Li ions at the 3a site is 90% or more is excellent in stoichiometry. Usually, in the lithium nickel composite oxide having a layered rock salt structure, transition metals, particularly Ni, are irregularly arranged in the Li layer, and Li is irregularly arranged in the transition metal layer. The smaller the irregular arrangement, the more stable the crystal structure.
層状岩塩構造を有するリチウムニッケル含有複合酸化物は、一般式：ＬｉａＣｏｐＮｉｑＭｎｒＤｓＯｘ（Ｄは、Ａｌ、Ｍｇ、Ｔｉ、Ｓｎ、Ｚｎ、Ｗ、Ｚｒ、Ｍｏ、Ｆｅ及びＮａから選ばれる少なくとも１つであり、ｐ＋ｑ＋ｒ＋ｓ＝１、０≦ｐ＜１、０＜ｑ＜１、０≦ｒ＜１、０≦ｓ＜１、０．８≦ａ＜２．０、−０．２≦ｘ−（ａ＋ｐ＋ｑ＋ｒ＋ｓ）≦０．２）で表される化合物であることが好ましい。リチウムニッケル含有複合酸化物として、例えば、ＬｉＮｉＯ２、ＬｉＮｉ０．８Ｃｏ０．２Ｏ２、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉ０．６Ｃｏ０．２Ｍｎ０．２Ｏ２、ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２が挙げられる。 Lithium-nickel-containing composite oxide having a layered rock salt structure represented by the general formula: Li a Co p Ni q Mn r D s O x (D is, Al, Mg, Ti, Sn , Zn, W, Zr, Mo, Fe and At least one selected from Na, p + q + r + s = 1, 0 ≦ p <1, 0 <q <1, 0 ≦ r <1, 0 ≦ s <1, 0.8 ≦ a <2.0, −0 .2 ≦ x− (a + p + q + r + s) ≦ 0.2) is preferable. Examples of the lithium nickel-containing composite oxide include LiNiO 2 , LiNi 0.8 Co 0.2 O 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.6 Co 0.2 Mn 0. 2 O 2, LiNi 0.5 Co 0.2 Mn 0.3 O 2 and the like.
層状岩塩構造を有するリチウムニッケル含有複合酸化物は、ＬｉＮｉＯ２のＮｉ位置の一部のＮｉをＣｏ及び／またはＭｎで置き換えた固溶体であることが好ましい。Ｎｉを、ＣｏまたはＭｎで置換することによって、リチウムニッケル含有複合酸化物は電池特性が向上する。特にリチウムニッケル含有複合酸化物としては、ＬｉＣｏ１／３Ｎｉ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉ０．６Ｃｏ０．２Ｍｎ０．２Ｏ２及びＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２が好ましい。 The lithium nickel-containing composite oxide having a layered rock salt structure is preferably a solid solution in which a portion of Ni in LiNiO 2 is replaced with Co and / or Mn. By replacing Ni with Co or Mn, the battery characteristics of the lithium nickel-containing composite oxide are improved. In particular, lithium nickel-containing composite oxides include LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 and LiNi 0.5 Co 0.2 Mn 0. .3 O 2 is preferred.
リチウムニッケル含有複合酸化物は、その平均粒径Ｄ５０が１μｍ〜２０μｍである粉末形状であることが好ましい。リチウムニッケル含有複合酸化物が粉末形状であると第１水溶液または第２水溶液と混合しやすい。その平均粒径Ｄ５０が１μｍより小さいとリチウムニッケル含有複合酸化物が凝集してしまうのでリチウムニッケル含有複合酸化物を混合しにくくなり、その平均粒径Ｄ５０が２０μｍより大きいと、個々のリチウムニッケル含有酸化物の内部まで処理されにくくなる。 Lithium-nickel-containing composite oxide preferably has an average particle diameter D 50 is a powder shape is 1 m to 20 m. When the lithium nickel-containing composite oxide is in a powder form, it is easy to mix with the first aqueous solution or the second aqueous solution. If the average particle diameter D 50 is smaller than 1 μm, the lithium nickel-containing composite oxide is aggregated, so that it becomes difficult to mix the lithium nickel-containing composite oxide. If the average particle diameter D 50 is larger than 20 μm, each lithium It becomes difficult to treat even the inside of the nickel-containing oxide.
第一工程は、上記のリチウムニッケル含有複合酸化物を第１水溶液または第２水溶液と混合して処理する工程である。第１水溶液はＺｒＯ（ＮＯ３）２・２Ｈ２Ｏと（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを含み、第２水溶液はＶＯＳＯ４と（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを含む。 The first step is a step in which the lithium nickel-containing composite oxide is mixed with the first aqueous solution or the second aqueous solution for treatment. The first aqueous solution contains ZrO (NO 3 ) 2 · 2H 2 O and (NH 4 ) 2 HPO 4 · 6H 2 O, and the second aqueous solution contains VOSO 4 and (NH 4 ) 2 HPO 4 · 6H 2 O. Including.
混合は、各水溶液に投入したリチウムニッケル含有複合酸化物を１分〜１２０分攪拌することによって行うことができる。 The mixing can be performed by stirring the lithium nickel-containing composite oxide charged into each aqueous solution for 1 minute to 120 minutes.
第１水溶液の場合、ＺｒＯ（ＮＯ３）２・２Ｈ２Ｏと（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを一定割合で純水中に溶解することによって第１水溶液を作成できる。この割合はＺｒ／Ｐ＝１／１０〜１０／１となるような割合であればよい。特にＺｒ／Ｐ＝１／１となるような割合であることが好ましい。 In the case of the first aqueous solution, the first aqueous solution can be prepared by dissolving ZrO (NO 3 ) 2 .2H 2 O and (NH 4 ) 2 HPO 4 .6H 2 O in pure water at a constant ratio. This ratio may be a ratio such that Zr / P = 1/10 to 10/1. In particular, the ratio is preferably such that Zr / P = 1/1.
また第１水溶液は、液中に（ＺｒＯ）２Ｐ２Ｏ７が析出していてもよい。第１水溶液には、ＺｒＯ２＋イオン、ＮＯ３ ―イオン、ＮＨ４ ―イオン、ＨＰＯ４ ２−イオン、Ｈ＋イオン、（ＺｒＯ）２Ｐ２Ｏ７、ＺｒＯ（ＮＯ３）２・２Ｈ２Ｏ及び（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏから選ばれる少なくとも１つが存在する。これらの各イオンまたは化合物がこの処理に対してどのような作用を奏しているかは不明である。 The first aqueous solution may have (ZrO) 2 P 2 O 7 precipitated in the liquid. The first aqueous solution includes ZrO 2+ ions, NO 3 − ions, NH 4 − ions , HPO 4 2− ions, H + ions, (ZrO) 2 P 2 O 7 , ZrO (NO 3 ) 2 .2H 2 O and There is at least one selected from (NH 4 ) 2 HPO 4 .6H 2 O. It is unclear what action each of these ions or compounds has on this treatment.
また第１水溶液の処理によって析出した（ＺｒＯ）２Ｐ２Ｏ７がリチウムニッケル複合酸化物の表面に付着することも考えられる。一般的に正極活物質の表面に付着物があるのは容量低下の原因になりうるので、第１水溶液とリチウムニッケル含有複合酸化物の混合比は、リチウムニッケル含有複合酸化物の質量を１００質量％としたときに水溶液中に析出すると計算される（ＺｒＯ）２Ｐ２Ｏ７が０．１質量％〜１０質量％となるように、混合するリチウムニッケル含有複合酸化物の質量を規定することが好ましい。 It is also conceivable that (ZrO) 2 P 2 O 7 precipitated by the treatment of the first aqueous solution adheres to the surface of the lithium nickel composite oxide. In general, since deposits on the surface of the positive electrode active material can cause a decrease in capacity, the mixing ratio of the first aqueous solution and the lithium nickel-containing composite oxide is 100 masses of the lithium nickel-containing composite oxide. The mass of the lithium-nickel-containing composite oxide to be mixed is regulated so that (ZrO) 2 P 2 O 7 is calculated to be 0.1 mass% to 10 mass%, which is calculated to precipitate in the aqueous solution. Is preferred.
第２水溶液の場合、ＶＯＳＯ４と（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを一定割合で純水中に溶解することによって第２水溶液を作成できる。この割合はＶ／Ｐ＝１／１０〜１０／１となるような割合であればよい。特にＶ／Ｐ＝１／２となるような割合であることが好ましい。 In the case of the second aqueous solution, the second aqueous solution can be prepared by dissolving VOSO 4 and (NH 4 ) 2 HPO 4 .6H 2 O in pure water at a constant ratio. This ratio may be a ratio such that V / P = 1/10 to 10/1. In particular, the ratio is preferably such that V / P = 1/2.
また第２水溶液は、液中にＶＯＰＯ４が析出していてもよい。従って第２水溶液には、ＶＯ２＋イオン、ＳＯ４ ２―イオン、ＮＨ４ ―イオン、ＨＰＯ４ ２−イオン、Ｈ＋イオン、ＶＯＰＯ４、ＶＯＳＯ４及び（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏから選ばれる少なくとも１つが存在する。これらの各イオンまたは化合物がこの処理に対してどのような作用を奏しているかは不明である。 In the second aqueous solution, VOPO 4 may be precipitated in the liquid. Therefore, the second aqueous solution includes VO 2+ ions, SO 4 2− ions, NH 4 − ions , HPO 4 2− ions, H + ions, VOPO 4 , VOSO 4 and (NH 4 ) 2 HPO 4 · 6H 2 O. There is at least one selected. It is unclear what action each of these ions or compounds has on this treatment.
また第２水溶液の処理によって析出したＶＯＰＯ４がリチウムニッケル複合酸化物の表面に付着することも考えられる。一般的に正極活物質の表面に付着物があるのは容量低下の原因になりうるので、第２水溶液とリチウムニッケル含有複合酸化物の混合比は、リチウムニッケル含有複合酸化物の質量を１００質量％としたときに水溶液中に析出すると計算されるＶＯＰＯ４が０．１質量％〜１０質量％となるように混合するリチウムニッケル含有複合酸化物の質量を規定することが好ましい。 It is also conceivable that VOPO 4 deposited by the treatment of the second aqueous solution adheres to the surface of the lithium nickel composite oxide. In general, since deposits on the surface of the positive electrode active material can cause a reduction in capacity, the mixing ratio of the second aqueous solution and the lithium nickel-containing composite oxide is 100 masses of the lithium nickel-containing composite oxide. It is preferable to define the mass of the lithium nickel-containing composite oxide to be mixed so that VOPO 4 calculated to be precipitated in the aqueous solution is 0.1 mass% to 10 mass%.
第一工程において、詳細は不明であるがリチウムニッケル含有複合酸化物の遷移金属層にある遷移金属が溶出すると推測している。 Although details are unknown in the first step, it is assumed that the transition metal in the transition metal layer of the lithium nickel-containing composite oxide elutes.
第一工程後で第二工程の前に濾過工程を有しても良い。濾過工程において、第一工程後の第１水溶液または第２水溶液から第一工程後のリチウムニッケル含有複合酸化物を濾過して取り出す。濾過は通常の方法によって処理液とリチウムニッケル含有複合酸化物とを分離し、濾過物であるリチウムニッケル含有複合酸化物を取り出せればよい。濾過は、吸引濾過してやるのが簡便である。 You may have a filtration process after the 1st process and before the 2nd process. In the filtration step, the lithium nickel-containing composite oxide after the first step is filtered out from the first aqueous solution or the second aqueous solution after the first step. The filtration may be performed by separating the treatment liquid and the lithium nickel-containing composite oxide by an ordinary method and taking out the lithium nickel-containing composite oxide as a filtrate. Filtration is easily performed by suction filtration.
第二工程において、第一工程後のリチウムニッケル含有複合酸化物を４００℃以上７００℃以下の温度で焼成する。焼成工程は１時間〜１０時間行えばよい。 In the second step, the lithium nickel-containing composite oxide after the first step is fired at a temperature of 400 ° C. or higher and 700 ° C. or lower. The firing step may be performed for 1 hour to 10 hours.
また第二工程の前にさらに乾燥工程を加えてもよい。乾燥工程においては、濾過物を１２０℃程度の温度の乾燥炉に入れて１時間〜１０時間乾燥すればよい。 Further, a drying step may be added before the second step. In the drying step, the filtrate may be placed in a drying furnace having a temperature of about 120 ° C. and dried for 1 to 10 hours.
第二工程において、詳細は不明であるが、リチウムニッケル含有複合酸化物のＬｉ層に混入したＮｉが遷移金属層に移動すると推測している。遷移金属層には上記第一工程によって溶出した遷移金属が占めていた空間が存在し、その空間にＮｉが移動すると推測する。これによりＬｉ層のＬｉの含有率があがる。 Although details are unknown in the second step, it is assumed that Ni mixed in the Li layer of the lithium nickel-containing composite oxide moves to the transition metal layer. It is assumed that the transition metal layer has a space occupied by the transition metal eluted in the first step, and Ni moves to the space. This increases the Li content of the Li layer.
上記第一工程と第二工程とを行うことによって、リチウムニッケル含有複合酸化物のＸ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率を高めることができる。本発明のリチウムニッケル含有複合酸化物の処理方法によってリチウムニッケル含有複合酸化物のＸ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率を高めることができる詳細な理由は不明である。 By performing the first step and the second step, the lithium content in the 3a site by the Rietveld analysis method by X-ray diffraction of the lithium nickel-containing composite oxide can be increased. The detailed reason why the lithium content in the 3a site by the Rietveld analysis by X-ray diffraction of the lithium nickel-containing composite oxide can be increased by the method for treating a lithium nickel-containing composite oxide of the present invention is unknown.
Ｘ線回折によるリートベルト解析法によれば、結晶構造、化学量論性がわかる。具体的にはこの解析によって、格子定数の他に結晶の完全性（化学量論性）の指標となる各イオンのサイト占有率を求めることができる。 According to the Rietveld analysis method by X-ray diffraction, the crystal structure and stoichiometry can be understood. Specifically, by this analysis, in addition to the lattice constant, the site occupancy of each ion that is an index of crystal perfection (stoichiometry) can be obtained.
Ｘ線回折によるリートベルト解析法とは、例えば、文献「粉末Ｘ線回折による材料分析」（１０８〜１２２頁、１９９３年６月１日、株式会社講談社サイエンティフィク発行）に記載されている方法であり、粉末Ｘ線回折の全パターンデータの格子定数や構造パラメーター等の関数を精密化し、解析を行なうものである。 The Rietveld analysis method by X-ray diffraction is, for example, the method described in the document “Material analysis by powder X-ray diffraction” (pages 108-122, June 1, 1993, published by Kodansha Scientific Co., Ltd.). The functions such as the lattice constants and the structural parameters of all the pattern data of powder X-ray diffraction are refined and analyzed.
リートベルト解析法の手順は以下に示す通りである。
Ａ．リートベルト解析法の手順
（１）粉末Ｘ線回折パターンのピークを指数づけし、空間群を絞り込む。
（２）最小２乗法あるいはＰａｗｌｅｙ法により格子定数を精密化する。
（３）結晶学的な知見及び化学組成等から大まかな原子配置を推定する。
（４）（３）で構築した構造モデルに基づいて、粉末Ｘ線回折図形をシミュレートする。
（５）リートベルト解析を行ない、３ａサイトに占めるリチウム含有量及び六方晶の層状化合物（空間群Ｒ−３ｍ）に属するリチウム複合酸化物の純度を測定する。
The procedure of the Rietveld analysis method is as follows.
A. Rietveld Analysis Procedure (1) Index the powder X-ray diffraction pattern peaks to narrow down the space group.
(2) Refine the lattice constant by the method of least squares or the Pawley method.
(3) Estimate the approximate atomic arrangement from crystallographic knowledge and chemical composition.
(4) Based on the structural model constructed in (3), a powder X-ray diffraction pattern is simulated.
(5) Rietveld analysis is performed to measure the lithium content in the 3a site and the purity of the lithium composite oxide belonging to the hexagonal layered compound (space group R-3m).
図１にＸ線回折パターンの一例を示す。図１は、後述するが、未処理である比較例１のリチウムニッケル含有複合酸化物の粉末Ｘ線回折測定法により測定したＸ線回折パターンを示す図である。このように各試料のそれぞれＸ線回折パターンを測定し、そこから上記したリートベルト解析法を行ってリートベルト解析法による３ａサイトに占めるリチウム含有率を算出できる。 FIG. 1 shows an example of an X-ray diffraction pattern. FIG. 1 is a diagram showing an X-ray diffraction pattern measured by a powder X-ray diffraction measurement method of an untreated lithium nickel-containing composite oxide of Comparative Example 1, which will be described later. In this manner, the X-ray diffraction pattern of each sample is measured, and the above-described Rietveld analysis method is performed therefrom to calculate the lithium content in the 3a site by the Rietveld analysis method.
＜リチウムイオン二次電池用正極活物質＞
本発明のリチウムイオン二次電池用正極活物質は、上記で記載したリチウムニッケル含有複合酸化物の処理方法で処理されたリチウムニッケル含有複合酸化物からなることを特徴とする。
<Positive electrode active material for lithium ion secondary battery>
The positive electrode active material for a lithium ion secondary battery of the present invention is characterized by comprising a lithium nickel-containing composite oxide treated by the above-described method for treating a lithium nickel-containing composite oxide.
上記で記載したリチウムニッケル含有複合酸化物の処理方法で処理されたリチウムニッケル含有複合酸化物は未処理のリチウムニッケル含有複合酸化物と比べてＸ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率が高い。 The lithium nickel-containing composite oxide treated by the above-described method for treating a lithium nickel-containing composite oxide is more lithium than the untreated lithium nickel-containing composite oxide in the 3a site according to the Rietveld analysis by X-ray diffraction. High content.
通常、層状岩塩構造のリチウムニッケル含有複合酸化物のＬｉ層には１割程度の不規則配列が存在する。この不規則配列は、主にＬｉ層にＮｉが不規則配列することによる。そのため、Ｌｉ層のＬｉの含有率が９０％程度となっている。このＬｉ層のＬｉの含有率が高くなれば、リチウムニッケル含有複合酸化物は、結晶構造が安定し、リチウムイオンが出入りしやすくなる。従って本発明のリチウムニッケル含有複合酸化物の処理方法で処理されたリチウムニッケル含有複合酸化物を正極活物質として用いると、リチウムイオン二次電池の放電容量が未処理のリチウムニッケル含有複合酸化物からなる正極活物質を用いたものより向上する。 Usually, about 10% of irregular arrangement exists in the Li layer of the lithium nickel-containing composite oxide having a layered rock salt structure. This irregular arrangement is mainly due to the irregular arrangement of Ni in the Li layer. Therefore, the Li content of the Li layer is about 90%. If the Li content in the Li layer is increased, the lithium nickel-containing composite oxide has a stable crystal structure and lithium ions can easily enter and exit. Therefore, when the lithium nickel-containing composite oxide treated by the method for treating a lithium nickel-containing composite oxide of the present invention is used as the positive electrode active material, the discharge capacity of the lithium ion secondary battery is from the untreated lithium nickel-containing composite oxide. It improves from the thing using the positive electrode active material which becomes.
ここで、本発明のリチウムニッケル含有複合酸化物の処理方法で処理されたリチウムニッケル含有複合酸化物は、表面の一部に一般式：（ＺｒＯ）２Ｐ２Ｏ７で表される化合物または一般式：ＶＯＰＯ４で表される化合物が付着していてもかまわない。 Here, the lithium nickel-containing composite oxide treated by the method for treating a lithium nickel-containing composite oxide of the present invention is a compound represented by the general formula: (ZrO) 2 P 2 O 7 or a part of the surface. A compound represented by the formula: VOPO 4 may be attached.
＜リチウムイオン二次電池＞
本発明のリチウムイオン二次電池は、上述したリチウムイオン二次電池用正極活物質を有する。
<Lithium ion secondary battery>
The lithium ion secondary battery of this invention has the positive electrode active material for lithium ion secondary batteries mentioned above.
正極は、上記リチウムイオン二次電池用正極活物質が結着剤で結着されてなる正極活物質層が、集電体に付着してなる。 The positive electrode is formed by adhering a positive electrode active material layer formed by binding the positive electrode active material for a lithium ion secondary battery with a binder to a current collector.
集電体は、リチウムイオン二次電池の放電又は充電の間、電極に電流を流し続けるための化学的に不活性な電子高伝導体をいう。集電体に用いることのできる材料として、例えばステンレス鋼、チタン、ニッケル、アルミニウム、銅などの金属材料または導電性樹脂を挙げることができる。また集電体は、箔、シート、フィルムなどの形態をとることができる。そのため、集電体として、例えば銅箔、ニッケル箔、アルミニウム箔、ステンレス箔などの金属箔を好適に用いることができる。 The current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharge or charging of a lithium ion secondary battery. Examples of materials that can be used for the current collector include metal materials such as stainless steel, titanium, nickel, aluminum, and copper, or conductive resins. The current collector can take the form of a foil, a sheet, a film, or the like. Therefore, metal foils, such as copper foil, nickel foil, aluminum foil, stainless steel foil, can be used suitably as a collector.
集電体は、その膜厚が１０μｍ〜１００μｍであることが好ましい。 The current collector preferably has a thickness of 10 μm to 100 μm.
正極活物質層はさらに導電助剤を含んでもよい。正極は、正極活物質および結着剤、並びに必要に応じて導電助剤を含む正極活物質層形成用組成物を調製し、さらにこの組成物に適当な溶剤を加えてペースト状にしてから、集電体の表面に塗布後、乾燥し、必要に応じて電極密度を高めるべく圧縮して形成することができる。 The positive electrode active material layer may further contain a conductive additive. The positive electrode is prepared by forming a positive electrode active material layer-forming composition containing a positive electrode active material and a binder and, if necessary, a conductive additive, and further adding a suitable solvent to the composition to make a paste. After applying to the surface of the current collector, it can be dried and compressed to increase the electrode density as necessary.
正極活物質層形成用組成物の塗布方法としては、ロールコート法、ディップコート法、ドクターブレード法、スプレーコート法、カーテンコート法などの従来から公知の方法を用いればよい。 As a method for applying the composition for forming a positive electrode active material layer, a conventionally known method such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method may be used.
粘度調整のための溶剤としては、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、メタノール、メチルイソブチルケトン（ＭＩＢＫ）などが使用可能である。 As a solvent for adjusting the viscosity, N-methyl-2-pyrrolidone (NMP), methanol, methyl isobutyl ketone (MIBK) and the like can be used.
結着剤は、上記正極活物質及び導電助剤を集電体に繋ぎ止める役割を果たすもので、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレンおよびフッ素ゴム等の含フッ素樹脂、ポリプロピレン、ポリエチレンおよびポリ酢酸ビニル系樹脂等の熱可塑性樹脂、ポリイミドおよびポリアミドイミド等のイミド系樹脂、アルコキシシリル基含有樹脂、並びにスチレンブタジエンゴム（ＳＢＲ）等のゴムを用いることができる。 The binder serves to bind the positive electrode active material and the conductive additive to the current collector. For example, the binder includes a fluorine-containing resin such as polyvinylidene fluoride, polytetrafluoroethylene and fluororubber, polypropylene, polyethylene and poly Thermoplastic resins such as vinyl acetate resins, imide resins such as polyimide and polyamideimide, alkoxysilyl group-containing resins, and rubbers such as styrene butadiene rubber (SBR) can be used.
導電助剤は、電極の導電性を高めるために添加される。導電助剤として、炭素質微粒子であるカーボンブラック、黒鉛、アセチレンブラック（ＡＢ）、ケッチェンブラック（登録商標）（ＫＢ）、気相法炭素繊維（ＶＧＣＦ）等を単独でまたは二種以上組み合わせて添加することができる。導電助剤の使用量については、特に限定的ではないが、例えば、正極に含有される活物質１００質量部に対して、１質量部〜３０質量部程度とすることができる。 The conductive assistant is added to increase the conductivity of the electrode. Carbon black, graphite, acetylene black (AB), ketjen black (registered trademark) (KB), vapor grown carbon fiber (VGCF), etc., which are carbonaceous fine particles, are used alone or in combination of two or more as conductive aids. Can be added. The amount of the conductive auxiliary agent used is not particularly limited, but can be, for example, about 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the active material contained in the positive electrode.
（その他の構成要素）
本発明のリチウムイオン二次電池は、電池構成要素として、上記した正極に加えて、負極、セパレータ、電解液を有する。
(Other components)
The lithium ion secondary battery of this invention has a negative electrode, a separator, and electrolyte solution in addition to the above-mentioned positive electrode as a battery component.
負極は、集電体と、集電体の表面に結着させた負極活物質層を有する。負極活物質層は、負極活物質、結着剤を含み、必要に応じて導電助剤を含む。集電体、結着剤、導電助剤は正極で説明したものと同様である。 The negative electrode has a current collector and a negative electrode active material layer bound to the surface of the current collector. A negative electrode active material layer contains a negative electrode active material and a binder, and contains a conductive support agent as needed. The current collector, binder and conductive additive are the same as those described for the positive electrode.
負極活物質としては、リチウムを吸蔵、放出可能な炭素系材料、リチウムと合金化可能な元素、リチウムと合金化可能な元素を有する化合物、あるいは高分子材料などを用いることができる。 As the negative electrode active material, a carbon-based material that can occlude and release lithium, an element that can be alloyed with lithium, a compound that includes an element that can be alloyed with lithium, a polymer material, or the like can be used.
炭素系材料としては、難黒鉛化性炭素、人造黒鉛、コークス類、グラファイト類、ガラス状炭素類、有機高分子化合物焼成体、炭素繊維、活性炭あるいはカーボンブラック類が挙げられる。ここで、有機高分子化合物焼成体とは、フェノール類やフラン類などの高分子材料を適当な温度で焼成して炭素化したものをいう。 Examples of the carbon-based material include non-graphitizable carbon, artificial graphite, coke, graphite, glassy carbon, organic polymer compound fired body, carbon fiber, activated carbon, or carbon black. Here, the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenols and furans at an appropriate temperature.
リチウムと合金化可能な元素は、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｆｒ、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｒａ、Ｔｉ、Ａｇ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉの少なくとも１種を有するとよい。中でも、リチウムと合金化可能な元素は、珪素（Ｓｉ）または錫（Ｓｎ）であるとよい。 Elements that can be alloyed with lithium are Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn. , Pb, Sb, Bi may be included. Among them, the element that can be alloyed with lithium is preferably silicon (Si) or tin (Sn).
リチウムと合金化可能な元素を有する化合物としては、例えば、ＺｎＬｉＡｌ、ＡｌＳｂ、ＳｉＢ４、ＳｉＢ６、Ｍｇ２Ｓｉ、Ｍｇ２Ｓｎ、Ｎｉ２Ｓｉ、ＴｉＳｉ２、ＭｏＳｉ２、ＣｏＳｉ２、ＮｉＳｉ２、ＣａＳｉ２、ＣｒＳｉ２、Ｃｕ５Ｓｉ、ＦｅＳｉ２、ＭｎＳｉ２、ＮｂＳｉ２、ＴａＳｉ２、ＶＳｉ２、ＷＳｉ２、ＺｎＳｉ２、ＳｉＣ、Ｓｉ３Ｎ４、Ｓｉ２Ｎ２Ｏ、ＳｉＯｖ（０＜ｖ≦２）、ＳｎＯｗ（０＜ｗ≦２）、ＳｎＳｉＯ３、ＬｉＳｉＯあるいはＬｉＳｎＯなどが使用できる。リチウムと合金化可能な元素を有する化合物としては、珪素化合物または錫化合物が好ましい。珪素化合物としては、ＳｉＯｘ（０．５≦ｘ≦１．５）が好ましい。錫化合物としては、例えば、スズ合金（Ｃｕ−Ｓｎ合金、Ｃｏ−Ｓｎ合金等）が使用できる。 Examples of the compound having an element that can be alloyed with lithium include ZnLiAl, AlSb, SiB 4 , SiB 6 , Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , and CaSi. 2, CrSi 2, Cu 5 Si , FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 <v ≦ 2), SnO w (0 <w ≦ 2), SnSiO 3 , LiSiO or LiSnO can be used. As the compound having an element that can be alloyed with lithium, a silicon compound or a tin compound is preferable. As the silicon compound, SiO x (0.5 ≦ x ≦ 1.5) is preferable. As the tin compound, for example, a tin alloy (Cu—Sn alloy, Co—Sn alloy, etc.) can be used.
高分子材料としては、ポリアセチレン、ポリピロールなどが使用できる。 As the polymer material, polyacetylene, polypyrrole, or the like can be used.
セパレータは正極と負極とを隔離し、両極の接触による電流の短絡を防止しつつ、リチウムイオンを通過させるものである。セパレータは、例えば、ポリテトラフルオロエチレン、ポリプロピレン、若しくはポリエチレンなどの合成樹脂製の多孔質膜、またはセラミックス製の多孔質膜が使用できる。 The separator separates the positive electrode and the negative electrode and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes. As the separator, for example, a porous film made of synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, or a porous film made of ceramics can be used.
電解液は、溶媒とこの溶媒に溶解された電解質とを含んでいる。 The electrolytic solution includes a solvent and an electrolyte dissolved in the solvent.
溶媒として、例えば、環状エステル類、鎖状エステル類、エーテル類が使用できる。環状エステル類として、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ガンマブチロラクトン、ビニレンカーボネート、２−メチル−ガンマブチロラクトン、アセチル−ガンマブチロラクトン、ガンマバレロラクトンが使用できる。鎖状エステル類として、例えば、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジプロピルカーボネート、メチルエチルカーボネート、プロピオン酸アルキルエステル、マロン酸ジアルキルエステル、酢酸アルキルエステルが使用できる。エーテル類として、例えば、テトラヒドロフラン、２−メチルテトラヒドロフラン、１，４−ジオキサン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、１，２−ジブトキシエタンが使用できる。 As the solvent, for example, cyclic esters, chain esters, and ethers can be used. Examples of cyclic esters include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone. Examples of the chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester. Examples of ethers that can be used include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane.
また上記電解液に溶解させる電解質として、例えば、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２等のリチウム塩を使用することができる。 Moreover, as an electrolyte dissolved in the electrolytic solution, for example, a lithium salt such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 can be used.
電解液として、例えば、エチレンカーボネート、ジメチルカーボネート、プロピレンカーボネート、ジメチルカーボネートなどの溶媒にＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３などのリチウム塩を０．５ｍｏｌ／ｌから１．７ｍｏｌ／ｌ程度の濃度で溶解させた溶液を使用することができる。 As the electrolytic solution, for example, a lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 in a solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, dimethyl carbonate, or the like is from 0.5 mol / l to 1.7 mol / l. A solution dissolved at a certain concentration can be used.
上記リチウムイオン二次電池は車両に搭載することができる。上記リチウムイオン二次電池は、優れた放電容量を有するため、そのリチウムイオン二次電池を搭載した車両は、出力の面で高性能となる。 The lithium ion secondary battery can be mounted on a vehicle. Since the lithium ion secondary battery has an excellent discharge capacity, a vehicle equipped with the lithium ion secondary battery has high performance in terms of output.
車両としては、電池による電気エネルギーを動力源の全部または一部に使用する車両であればよく、例えば、電気自動車、ハイブリッド自動車、プラグインハイブリッド自動車、ハイブリッド鉄道車両、電動フォークリフト、電気車椅子、電動アシスト自転車、電動二輪車が挙げられる。 The vehicle may be a vehicle that uses electric energy from a battery as a whole or a part of a power source. For example, an electric vehicle, a hybrid vehicle, a plug-in hybrid vehicle, a hybrid railway vehicle, an electric forklift, an electric wheelchair, and an electric assist. Bicycles and electric motorcycles are examples.
以上、本発明のリチウムニッケル含有複合酸化物の処理方法及びリチウムイオン二次電池用正極活物質およびそれを有するリチウムイオン二次電池の実施形態を説明したが、本発明は、上記実施形態に限定されるものではない。本発明の要旨を逸脱しない範囲において、当業者が行い得る変更、改良等を施した種々の形態にて実施することができる。 The embodiments of the method for treating a lithium nickel-containing composite oxide, the positive electrode active material for a lithium ion secondary battery, and the lithium ion secondary battery having the same have been described above, but the present invention is limited to the above embodiment. Is not to be done. The present invention can be implemented in various forms without departing from the gist of the present invention, with modifications and improvements that can be made by those skilled in the art.
以下、実施例を挙げて本発明を更に詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
＜リチウムニッケル含有複合酸化物の処理の準備＞
リチウムニッケル含有複合酸化物として平均粒径Ｄ５０が５μｍのＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を準備した。処理液の材料として、純水と、ＺｒＯ（ＮＯ３）２・２Ｈ２Ｏと、（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏと、ＶＯＳＯ４と、（ＮＨ４）２ＨＰＯ４・６Ｈ２Ｏとを準備した。
<Preparation for treatment of lithium nickel-containing composite oxide>
LiNi 0.5 Co 0.2 Mn 0.3 O 2 having an average particle diameter D 50 of 5 μm was prepared as a lithium nickel-containing composite oxide. As materials for the treatment liquid, pure water, ZrO (NO 3 ) 2 .2H 2 O, (NH 4 ) 2 HPO 4 .6H 2 O, VOSO 4 , (NH 4 ) 2 HPO 4 .6H 2 O And prepared.
＜第１水溶液の作成＞
純水中にＺｒＯ（ＮＯ３）２・２Ｈ２Ｏと（ＮＨ４）２ＨＰＯ４・６Ｈ２ＯとをＺｒ／Ｐ＝１／１となるように入れ、攪拌した。攪拌時間は１時間とした。
<Preparation of first aqueous solution>
ZrO (NO 3 ) 2 · 2H 2 O and (NH 4 ) 2 HPO 4 · 6H 2 O were placed in pure water so that Zr / P = 1/1 and stirred. The stirring time was 1 hour.
＜第２水溶液の作成＞
純水中にＶＯＳＯ４と（ＮＨ４）２ＨＰＯ４・６Ｈ２ＯとをＶ／Ｐ＝１／２となるように入れ、攪拌した。攪拌時間は１時間とした。
<Preparation of second aqueous solution>
VOSO 4 and (NH 4 ) 2 HPO 4 · 6H 2 O were put in pure water so that V / P = 1/2 and stirred. The stirring time was 1 hour.
＜リチウムニッケル含有複合酸化物の３ａサイトのリチウム含有率の測定＞
未処理のＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２の粉末Ｘ線回折測定法によりＸ線回折パターンを測定した。
<Measurement of lithium content at 3a site of lithium nickel-containing composite oxide>
An X-ray diffraction pattern was measured by powder X-ray diffraction measurement of untreated LiNi 0.5 Co 0.2 Mn 0.3 O 2 .
Ｘ線回折測定は、Ｘ線源はＣｕＫα（波長λ＝１．５４０５Å）を用いて、管電圧４０ｋＶ、電流２００ｍＡとし、発散スリット１．０°、散乱スリット１．０°、受光スリット０．１５ｍｍとした。測定した反射角度は１０°≦２θ≦１００°、走査角度は０．０２°で測定した。得られたＸ線回折結果に対し、ＰＤＸＬ ｖ２．０（リガク社製）を用いてリートベルト解析を行い、各金属元素成分のサイト占有率を求めた。 In the X-ray diffraction measurement, the X-ray source is CuKα (wavelength λ = 1.5405 mm), the tube voltage is 40 kV, the current is 200 mA, the divergence slit is 1.0 °, the scattering slit is 1.0 °, and the light receiving slit is 0.15 mm. It was. The measured reflection angle was 10 ° ≦ 2θ ≦ 100 °, and the scanning angle was 0.02 °. The obtained X-ray diffraction results were subjected to Rietveld analysis using PDXL v2.0 (manufactured by Rigaku Corporation) to determine the site occupancy ratio of each metal element component.
図１に未処理である比較例１のリチウムニッケル含有複合酸化物の粉末Ｘ線回折測定法により測定したＸ線回折パターンを示す。このＸ線回折パターンを元に上記したリートベルト解析を行ない、３ａサイトに占めるリチウム含有量を測定した。 FIG. 1 shows an X-ray diffraction pattern measured by a powder X-ray diffraction measurement method of an untreated lithium nickel-containing composite oxide of Comparative Example 1. The Rietveld analysis described above was performed based on this X-ray diffraction pattern, and the lithium content in the 3a site was measured.
その結果、未処理のＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２のリチウム含有率（％）は９５．９％であった。この未処理のＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を比較例１の正極活物質とする。 As a result, the lithium content (%) of untreated LiNi 0.5 Co 0.2 Mn 0.3 O 2 was 95.9%. The LiNi 0.5 Co 0.2 Mn 0.3 O 2 of the untreated and positive electrode active material of Comparative Example 1.
なお以下に示す各実施例及び比較例について同様に粉末Ｘ線回折測定法によりＸ線回折パターンを測定した。各Ｘ線回折パターンを元に上記したリートベルト解析を行ない、３ａサイトに占めるリチウム含有量を測定した。一例として、図２に後述する実施例２の処理方法で処理されたリチウムニッケル含有複合酸化物の粉末Ｘ線回折測定法により測定したＸ線回折パタ−ンを示す。また図３に後述する実施例６の処理方法で処理されたリチウムニッケル含有複合酸化物の粉末Ｘ線回折測定法により測定したＸ線回折パタ−ンを示す。 In addition, about each Example and comparative example shown below, the X-ray-diffraction pattern was similarly measured by the powder X-ray-diffraction measuring method. The Rietveld analysis described above was performed based on each X-ray diffraction pattern, and the lithium content in the 3a site was measured. As an example, FIG. 2 shows an X-ray diffraction pattern measured by a powder X-ray diffraction measurement method of a lithium nickel-containing composite oxide processed by the processing method of Example 2 described later. FIG. 3 shows an X-ray diffraction pattern measured by a powder X-ray diffraction measurement method of a lithium nickel-containing composite oxide processed by the processing method of Example 6 described later.
図１、図２及び図３を比較すると、そのＸ線回折パターンはよく似ていた。このことから実施例２及び実施例６の処理方法で処理された正極活物質の結晶構造と、未処理の正極活物質の結晶構造とには大幅な違いはないことが推測された。また、他の実施例及び比較例もＸ線回折パターンを取得した。そのＸ線回折パターンは、図１、図２及び図３に示すＸ線回折パターンとよく似ていた。そのため他の各実施例及び比較例のＸ線回折パターンについては記載を省略する。 Comparing FIGS. 1, 2 and 3, the X-ray diffraction patterns were very similar. From this, it was speculated that there was no significant difference between the crystal structure of the positive electrode active material treated by the treatment methods of Example 2 and Example 6 and the crystal structure of the untreated positive electrode active material. In addition, X-ray diffraction patterns were also obtained in other examples and comparative examples. The X-ray diffraction pattern was very similar to the X-ray diffraction patterns shown in FIGS. Therefore, description is abbreviate | omitted about the X-ray-diffraction pattern of each other Example and a comparative example.
（実施例１の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときに第１水溶液中に析出すると考えられる（ＺｒＯ）２Ｐ２Ｏ７が０．１質量％となるように第１水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入し、室温で１時間攪拌した。溶液を吸引濾過し、スラリー状の濾過物を１２０℃の乾燥機で１２時間乾燥した。塊状になった乾燥後の濾過物を乳棒および乳鉢を用いて粉砕し、坩堝にいれて４００℃で５時間焼成した。焼成物を乳棒および乳鉢を用いて粉砕し、実施例１の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを実施例１の正極活物質とする。実施例１の正極活物質の３ａサイトのリチウム含有率は９６．３％であった。
(Processing method of Example 1)
When LiNi 0.5 Co 0.2 Mn 0.3 O 2 is 100% by mass, it is considered that (ZrO) 2 P 2 O 7 is 0.1% by mass, which is considered to precipitate in the first aqueous solution. LiNi 0.5 Co 0.2 Mn 0.3 O 2 was added to one aqueous solution and stirred at room temperature for 1 hour. The solution was subjected to suction filtration, and the slurry-like filtrate was dried with a dryer at 120 ° C. for 12 hours. The dried filtrate that had become agglomerated was pulverized using a pestle and mortar, placed in a crucible, and baked at 400 ° C. for 5 hours. The fired product was pulverized using a pestle and a mortar to obtain LiNi 0.5 Co 0.2 Mn 0.3 O 2 treated by the treatment method of Example 1. This is designated as the positive electrode active material of Example 1. The lithium content of the 3a site of the positive electrode active material of Example 1 was 96.3%.
（実施例２の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときに第１水溶液中に析出すると考えられる（ＺｒＯ）２Ｐ２Ｏ７が０．５質量％となるように第１水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入した以外は実施例１の処理方法と同様にして、実施例２の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを実施例２の正極活物質とする。実施例２の正極活物質の３ａサイトのリチウム含有率は９６．９％であった。
(Processing method of Example 2)
When the amount of LiNi 0.5 Co 0.2 Mn 0.3 O 2 is 100% by mass, the (ZrO) 2 P 2 O 7 that is considered to precipitate in the first aqueous solution is 0.5% by mass. LiNi 0.5 Co 0. 0 treated by the treatment method of Example 2 in the same manner as in the treatment method of Example 1, except that LiNi 0.5 Co 0.2 Mn 0.3 O 2 was added to one aqueous solution . 2 Mn 0.3 O 2 was obtained. This is designated as the positive electrode active material of Example 2. The lithium content of the 3a site of the positive electrode active material of Example 2 was 96.9%.
（実施例３の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときに第１水溶液中に析出すると考えられる（ＺｒＯ）２Ｐ２Ｏ７が１質量％となるように第１水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入した以外は実施例１の処理方法と同様にして、実施例３の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを実施例３の正極活物質とする。実施例３の正極活物質の３ａサイトのリチウム含有率は９６．９％であった。
(Processing method of Example 3)
When the LiNi 0.5 Co 0.2 Mn 0.3 O 2 is 100 mass%, the first aqueous solution is such that (ZrO) 2 P 2 O 7 is considered to precipitate in the first aqueous solution at 1 mass%. the LiNi 0.5 Co 0.2 Mn 0.3 O 2 except that the turned on in the same manner as the processing method of example 1, LiNi 0.5 Co 0.2 were processed in the processing method of example 3 Mn 0.3 O 2 was obtained. This is designated as the positive electrode active material of Example 3. The lithium content of the 3a site of the positive electrode active material of Example 3 was 96.9%.
（実施例４の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときに第２水溶液中に析出すると考えられるＶＯＰＯ４が０．１質量％となるように第２水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入し、１時間攪拌した。溶液を吸引濾過し、スラリー状の濾過物を１２０℃の乾燥機で１２時間乾燥した。塊状になった乾燥後の濾過物を乳棒および乳鉢を用いて粉砕し、坩堝にいれて７００℃で５時間焼成した。焼成物を乳棒および乳鉢を用いて粉砕し、実施例４の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを実施例４の正極活物質とする。実施例４の正極活物質の３ａサイトのリチウム含有率は９６．６％であった。
(Processing method of Example 4)
LiNi 0.5 Co 0.2 Mn 0.3 O 2 was added to the second aqueous solution so that the amount of VOPO 4 that would be precipitated in the second aqueous solution was 0.1% by mass when the content of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was 100% by mass . 5 Co 0.2 Mn 0.3 O 2 was added and stirred for 1 hour. The solution was subjected to suction filtration, and the slurry-like filtrate was dried with a dryer at 120 ° C. for 12 hours. The dried filtrate that had become agglomerated was pulverized using a pestle and mortar, placed in a crucible, and baked at 700 ° C. for 5 hours. The fired product was pulverized using a pestle and a mortar to obtain LiNi 0.5 Co 0.2 Mn 0.3 O 2 treated by the treatment method of Example 4. This is designated as the positive electrode active material of Example 4. The lithium content of the 3a site of the positive electrode active material of Example 4 was 96.6%.
（実施例５の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときに第２水溶液中に析出すると考えられるＶＯＰＯ４が０．５質量％となるように第２水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入した以外は実施例４の処理方法と同様にして、実施例５の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを実施例５の正極活物質とする。実施例５の正極活物質の３ａサイトのリチウム含有率は９６．７％であった。
(Processing method of Example 5)
LiNi 0.5 Co 0.2 Mn 0.3 O 2 was added to the second aqueous solution so that the amount of VOPO 4 that would be precipitated in the second aqueous solution was 0.5% by mass when the content of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was 100% by mass . LiNi 0.5 Co 0.2 Mn 0.3 O treated by the treatment method of Example 5 in the same manner as the treatment method of Example 4 except that 5 Co 0.2 Mn 0.3 O 2 was added. 2 was obtained. This is designated as the positive electrode active material of Example 5. The lithium content of the 3a site of the positive electrode active material of Example 5 was 96.7%.
（実施例６の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときに第２水溶液中に析出すると考えられるＶＯＰＯ４が１質量％となるように第２水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入した以外は実施例４の処理方法と同様にして、実施例６の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを実施例６の正極活物質とする。実施例６の正極活物質の３ａサイトのリチウム含有率は９６．８％であった。
(Processing method of Example 6)
LiNi 0.5 Co 0.2 Mn 0.3 LiNi O 2 to the second aqueous solution so VOPO 4 thought to precipitate in the second aqueous solution is 1 wt% is 100 mass% 0.5 Co LiNi 0.5 Co 0.2 Mn 0.3 O 2 treated by the treatment method of Example 6 was used in the same manner as the treatment method of Example 4 except that 0.2 Mn 0.3 O 2 was added. Obtained. This is designated as the positive electrode active material of Example 6. The lithium content of the 3a site of the positive electrode active material of Example 6 was 96.8%.
（比較例２の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときに第２水溶液中に析出すると考えられるＶＯＰＯ４が０．１質量％となるように第２水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入し、１時間攪拌した。溶液を吸引濾過し、スラリー状の濾過物を１２０℃の乾燥機で５時間乾燥した。塊状になった乾燥後の濾過物を乳棒および乳鉢を用いて粉砕し、比較例２の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを比較例２の正極活物質とする。比較例２の正極活物質の３ａサイトのリチウム含有率は９６．１％であった。
(Treatment method of Comparative Example 2)
LiNi 0.5 Co 0.2 Mn 0.3 O 2 was added to the second aqueous solution so that the amount of VOPO 4 that would be precipitated in the second aqueous solution was 0.1% by mass when the content of LiNi 0.5 Co 0.2 Mn 0.3 O 2 was 100% by mass . 5 Co 0.2 Mn 0.3 O 2 was added and stirred for 1 hour. The solution was suction filtered, and the slurry-like filtrate was dried with a 120 ° C. dryer for 5 hours. The dried filtrate in the form of lumps was pulverized using a pestle and mortar to obtain LiNi 0.5 Co 0.2 Mn 0.3 O 2 treated by the treatment method of Comparative Example 2. This is designated as the positive electrode active material of Comparative Example 2. The lithium content of the 3a site of the positive electrode active material of Comparative Example 2 was 96.1%.
（比較例３の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときにＶＯＰＯ４が０．５質量％となるように第２水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入した以外は比較例２の処理方法と同様にして、比較例３の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを比較例３の正極活物質とする。比較例３の正極活物質の３ａサイトのリチウム含有率は９６．１％であった。
(Treatment method of Comparative Example 3)
LiNi 0.5 Co 0.2 Mn 0.3 O 2 to the second aqueous solution so VOPO 4 is 0.5 wt% is 100 wt% LiNi 0.5 Co 0.2 Mn 0.3 except that the O 2 was charged in the same manner as the processing method of the comparative example 2, to obtain a LiNi 0.5 Co 0.2 Mn 0.3 O 2 which has been processed by the processing method of the comparative example 3. This is designated as the positive electrode active material of Comparative Example 3. The lithium content of the 3a site of the positive electrode active material of Comparative Example 3 was 96.1%.
（比較例４の処理方法）
ＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を１００質量％としたときにＶＯＰＯ４が１質量％となるように第２水溶液にＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を投入した以外は比較例２の処理方法と同様にして、比較例４の処理方法で処理されたＬｉＮｉ０．５Ｃｏ０．２Ｍｎ０．３Ｏ２を得た。これを比較例４の正極活物質とする。比較例４の正極活物質の３ａサイトのリチウム含有率は９５．９％であった。
(Treatment method of Comparative Example 4)
LiNi 0.5 Co 0.2 Mn 0.3 LiNi O 2 to the second aqueous solution so VOPO 4 becomes 1% by mass is 100 wt% 0.5 Co 0.2 Mn 0.3 O 2 LiNi 0.5 Co 0.2 Mn 0.3 O 2 treated by the treatment method of Comparative Example 4 was obtained in the same manner as the treatment method of Comparative Example 2 except that was added. This is referred to as a positive electrode active material of Comparative Example 4. The lithium content of the 3a site of the positive electrode active material of Comparative Example 4 was 95.9%.
各処理方法で処理された正極活物質の処理液の種類、配合割合、焼成温度、Ｘ線回折によるリートベルト解析法による３ａサイトに占めるリチウム含有率を表１にまとめて示す。 Table 1 summarizes the types of the treatment liquid of the positive electrode active material treated by each treatment method, the mixing ratio, the firing temperature, and the lithium content in the 3a site by the Rietveld analysis method by X-ray diffraction.
表１からわかるように、実施例１〜実施例６の正極活物質の３ａサイトに占めるリチウム含有率は、比較例１の正極活物質の３ａサイトに占めるリチウム含有率と比較して大きくなった。また比較例２〜比較例４の正極活物質の３ａサイトに占めるリチウム含有率は、比較例１の正極活物質の３ａサイトに占めるリチウム含有率と変わらないことから、本発明のリチウムニッケル含有複合酸化物の処理方法には、第一工程だけではなく第一工程と第二工程の両方が必要であることがわかった。 As can be seen from Table 1, the lithium content in the 3a site of the positive electrode active materials of Examples 1 to 6 was larger than the lithium content in the 3a site of the positive electrode active material of Comparative Example 1. . Further, the lithium content in the 3a site of the positive electrode active material of Comparative Examples 2 to 4 is not different from the lithium content in the 3a site of the positive electrode active material of Comparative Example 1, and thus the lithium nickel-containing composite of the present invention. It was found that the oxide treatment method requires not only the first step but also both the first step and the second step.
上記の結果から第一工程において、リチウムニッケル含有複合酸化物の遷移金属層にある遷移金属が溶出し、第二工程において、リチウムニッケル含有複合酸化物のＬｉ層に混入したＮｉが遷移金属層に移動し、Ｌｉ層のＮｉの含有率が下がって、Ｌｉの含有率が上がったのだと推測できる。 From the above results, in the first step, the transition metal in the transition metal layer of the lithium nickel-containing composite oxide is eluted, and in the second step, Ni mixed in the Li layer of the lithium nickel-containing composite oxide becomes the transition metal layer. It can be presumed that the Ni content in the Li layer decreased and the Li content increased.
［ラミネート型リチウムイオンリチウムイオン二次電池の作製］
（実施例１のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池を次のようにして作製した。
[Production of laminated lithium ion lithium ion secondary battery]
(Laminated lithium ion secondary battery of Example 1)
The laminated lithium ion secondary battery of Example 1 was produced as follows.
まず実施例１の正極活物質と導電助剤としてアセチレンブラックと、結着剤としてポリフッ化ビニリデン（ＰＶＤＦ）とを、それぞれ９４質量部、３質量部、３質量部の割合で混合し、この混合物を適量のＮ−メチル−２−ピロリドン（ＮＭＰ）に分散させて、スラリーを作製した。 First, the positive electrode active material of Example 1, acetylene black as a conductive additive, and polyvinylidene fluoride (PVDF) as a binder were mixed in a ratio of 94 parts by mass, 3 parts by mass, and 3 parts by mass, respectively. Was dispersed in an appropriate amount of N-methyl-2-pyrrolidone (NMP) to prepare a slurry.
集電体として厚み２０μｍのアルミニウム箔を準備した。上記集電体の表面にドクターブレードを用いて、スラリーを膜状に塗布した。スラリーが塗布された集電体を８０℃で２０分間乾燥してＮＭＰを揮発させて除去した後、ロ−ルプレス機により、プレスして接合物を得た。ここで、正極活物質層の密度は１２ｇ／ｃｍ２となるようにした。接合物を１２０℃で６時間、真空乾燥機で加熱した後、所定の形状（２５ｍｍ×３０ｍｍの矩形状）に切り取り、厚さ６０μm程度の正極とした。 An aluminum foil having a thickness of 20 μm was prepared as a current collector. The slurry was applied in a film form on the surface of the current collector using a doctor blade. The current collector coated with the slurry was dried at 80 ° C. for 20 minutes to volatilize and remove NMP, and then pressed by a roll press to obtain a bonded product. Here, the density of the positive electrode active material layer was set to 12 g / cm 2 . The joined product was heated with a vacuum dryer at 120 ° C. for 6 hours, and then cut into a predetermined shape (rectangular shape of 25 mm × 30 mm) to obtain a positive electrode having a thickness of about 60 μm.
負極は以下のように作製した。黒鉛粉末９７質量部と、導電助剤としてアセチレンブラック１質量部と、結着剤として、スチレン−ブタジエンゴム（ＳＢＲ）１質量部、カルボキシメチルセルロース（ＣＭＣ）１質量部とを混合した。この混合物を適量のイオン交換水に分散させてスラリーを作製した。このスラリーを負極用集電体である厚み２０μｍの銅箔にドクターブレードを用いて膜状になるように塗布した。スラリーが塗布された集電体を８０℃で２０分間乾燥してＮＭＰを揮発させて除去した後、ロ−ルプレス機により、プレスして接合物を得た。接合物を２００℃で２時間、真空乾燥機で加熱した。加熱後の接合物を、所定の形状（２５ｍｍ×３０ｍｍの矩形状）に切り取り、負極とした。負極の厚さは４５μｍ程度であった。 The negative electrode was produced as follows. 97 parts by mass of graphite powder, 1 part by mass of acetylene black as a conductive additive, 1 part by mass of styrene-butadiene rubber (SBR) and 1 part by mass of carboxymethylcellulose (CMC) as a binder were mixed. This mixture was dispersed in an appropriate amount of ion-exchanged water to prepare a slurry. This slurry was applied to a copper foil having a thickness of 20 μm, which is a negative electrode current collector, in a film shape using a doctor blade. The current collector coated with the slurry was dried at 80 ° C. for 20 minutes to volatilize and remove NMP, and then pressed by a roll press to obtain a bonded product. The bonded product was heated in a vacuum dryer at 200 ° C. for 2 hours. The bonded product after heating was cut into a predetermined shape (rectangular shape of 25 mm × 30 mm) to obtain a negative electrode. The thickness of the negative electrode was about 45 μm.
上記の正極および負極を用いて、ラミネート型リチウムイオン二次電池を製作した。詳しくは、正極１および負極の間に、セパレータとしてポリプロピレン樹脂からなる矩形状シート（２７×３２ｍｍ、厚さ２５μｍ）を挟装して極板群とした。この極板群を二枚一組のラミネートフィルムで覆い、三辺をシールした後、袋状となったラミネートフィルムに電解液を注入した。電解液としてエチレンカーボネート（ＥＣ）とジエチルカーボネー（ＤＥＣ）をＥＣ：ＤＥＣ＝３：７（体積比）で混合した溶媒に１モルのＬｉＰＦ6を溶解した溶液を用いた。その後、残りの一辺をシールすることで、四辺が気密にシールされ、極板群および電解液が密閉されたラミネート型リチウムイオン二次電池を得た。なお、正極および負極は外部と電気的に接続可能なタブを備え、このタブの一部はラミネート型リチウムイオン二次電池の外側に延出している。以上の工程で、実施例１のラミネート型リチウムイオン二次電池を作製した。 A laminate type lithium ion secondary battery was manufactured using the positive electrode and the negative electrode. Specifically, a rectangular sheet (27 × 32 mm, thickness 25 μm) made of polypropylene resin as a separator was sandwiched between the positive electrode 1 and the negative electrode to form an electrode plate group. The electrode plate group was covered with a set of two laminated films, and the three sides were sealed, and then an electrolyte solution was injected into the bag-like laminated film. As an electrolytic solution, a solution obtained by dissolving 1 mol of LiPF 6 in a solvent obtained by mixing ethylene carbonate (EC) and diethyl carbonate (DEC) at EC: DEC = 3: 7 (volume ratio) was used. Thereafter, the remaining one side was sealed to obtain a laminate type lithium ion secondary battery in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed. Note that the positive electrode and the negative electrode have a tab that can be electrically connected to the outside, and a part of the tab extends to the outside of the laminated lithium ion secondary battery. The laminated lithium ion secondary battery of Example 1 was produced through the above steps.
（実施例２のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を実施例２の正極活物質とした以外は実施例１と同様にして、実施例２のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Example 2)
A laminated lithium ion secondary battery of Example 2 was produced in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Example 2 in the laminated lithium ion secondary battery of Example 1. .
（実施例３のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を実施例３の正極活物質とした以外は実施例１と同様にして、実施例３のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Example 3)
A laminated lithium ion secondary battery of Example 3 was produced in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Example 3 in the laminated lithium ion secondary battery of Example 1. .
（実施例４のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を実施例４の正極活物質とした以外は実施例１と同様にして、実施例４のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Example 4)
A laminated lithium ion secondary battery of Example 4 was produced in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Example 4 in the laminated lithium ion secondary battery of Example 1. .
（実施例５のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を実施例５の正極活物質とした以外は実施例１と同様にして、実施例５のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Example 5)
A laminated lithium ion secondary battery of Example 5 was produced in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Example 5 in the laminated lithium ion secondary battery of Example 1. .
（実施例６のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を実施例６の正極活物質とした以外は実施例１と同様にして、実施例６のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Example 6)
A laminated lithium ion secondary battery of Example 6 was produced in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Example 6 in the laminated lithium ion secondary battery of Example 1. .
（比較例１のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を比較例１の正極活物質とした以外は実施例１と同様にして、比較例１のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Comparative Example 1)
A laminated lithium ion secondary battery of Comparative Example 1 was prepared in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Comparative Example 1 in the laminated lithium ion secondary battery of Example 1. .
（比較例２のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を比較例２の正極活物質とした以外は実施例１と同様にして、比較例２のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Comparative Example 2)
A laminated lithium ion secondary battery of Comparative Example 2 was produced in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Comparative Example 2 in the laminated lithium ion secondary battery of Example 1. .
（比較例３のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を比較例３の正極活物質とした以外は実施例１と同様にして、比較例３のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Comparative Example 3)
A laminated lithium ion secondary battery of Comparative Example 3 was produced in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Comparative Example 3 in the laminated lithium ion secondary battery of Example 1. .
（比較例４のラミネート型リチウムイオン二次電池）
実施例１のラミネート型リチウムイオン二次電池において、正極活物質を比較例４の正極活物質とした以外は実施例１と同様にして、比較例４のラミネート型リチウムイオン二次電池を作製した。
(Laminated lithium ion secondary battery of Comparative Example 4)
A laminated lithium ion secondary battery of Comparative Example 4 was prepared in the same manner as in Example 1 except that the positive electrode active material was changed to the positive electrode active material of Comparative Example 4 in the laminated lithium ion secondary battery of Example 1. .
＜初期放電容量測定＞
実施例１〜６及び比較例１〜４のラミネート型リチウムイオン二次電池を用いて初期放電容量を測定した。
<Initial discharge capacity measurement>
The initial discharge capacity was measured using the laminate type lithium ion secondary batteries of Examples 1 to 6 and Comparative Examples 1 to 4.
初期放電容量測定は以下のように行った。充電は室温で１Ｃレート、電圧４．５ＶまでＣＣ充電（定電流充電）をした後、電圧４．５Ｖで１．５時間ＣＶ充電（定電圧充電）をした。放電は電圧３．０Ｖまで、０．３３ＣレートでＣＣ放電(定電流放電)を行い、電圧３．０Ｖで２時間ＣＶ放電をして放電容量を測定し、初期放電容量とした。 The initial discharge capacity was measured as follows. The charge was CC charge (constant current charge) to 1C rate and voltage 4.5V at room temperature, and then CV charge (constant voltage charge) for 1.5 hours at voltage 4.5V. Discharge was performed by CC discharge (constant current discharge) at a rate of 0.33 C up to a voltage of 3.0 V, CV discharge was performed at a voltage of 3.0 V for 2 hours, and the discharge capacity was measured to obtain an initial discharge capacity.
結果を表２にまとめた。 The results are summarized in Table 2.
表２からわかるように、実施例１〜実施例６のラミネート型リチウムイオン二次電池の初期放電容量は、比較例１のラミネート型リチウムイオン二次電池の初期放電容量よりも高くなった。このことから、本発明のリチウムニッケル含有複合酸化物の処理方法で処理されて、３ａサイトに占めるリチウム含有率が高くなった正極活物質を用いると、リチウムイオン二次電池の初期放電容量を向上できることがわかった。 As can be seen from Table 2, the initial discharge capacities of the laminated lithium ion secondary batteries of Examples 1 to 6 were higher than the initial discharge capacity of the laminated lithium ion secondary battery of Comparative Example 1. From this, when the positive electrode active material which is processed by the method for processing a lithium nickel-containing composite oxide of the present invention and has a high lithium content in the 3a site is used, the initial discharge capacity of the lithium ion secondary battery is improved. I knew it was possible.
Claims (5)
前記第一工程後のリチウムニッケル含有複合酸化物を４００℃以上７００℃以下の温度で焼成する第二工程と、
を有することを特徴とするリチウムニッケル含有複合酸化物の処理方法。 A lithium nickel-containing composite oxide having a layered rock salt structure is made of a first aqueous solution containing ZrO (NO 3 ) 2 .2H 2 O and (NH 4 ) 2 HPO 4 .6H 2 O or VOSO 4 and (NH 4 ) 2 HPO. A first step of treating with a second aqueous solution containing 4 · 6H 2 O;
A second step of firing the lithium nickel-containing composite oxide after the first step at a temperature of 400 ° C. or higher and 700 ° C. or lower;
A method for treating a lithium-nickel-containing composite oxide, comprising:
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