JP5360407B2 - Method for producing lithium transition metal composite oxide - Google Patents
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- JP5360407B2 JP5360407B2 JP2009250622A JP2009250622A JP5360407B2 JP 5360407 B2 JP5360407 B2 JP 5360407B2 JP 2009250622 A JP2009250622 A JP 2009250622A JP 2009250622 A JP2009250622 A JP 2009250622A JP 5360407 B2 JP5360407 B2 JP 5360407B2
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本発明は、リチウム遷移金属複合酸化物の製造方法、特に、層状岩塩構造を有するリチウム遷移金属複合酸化物の製造方法に関する。 The present invention relates to a method for producing a lithium transition metal composite oxide, and more particularly to a method for producing a lithium transition metal composite oxide having a layered rock salt structure.
近年、ポータブル機器や自動車などの電源として、小型・軽量であって高いエネルギー密度を有する非水電解質二次電池の需要が急速に伸びている。中でも、正極にリチウム遷移金属複合酸化物を用いたリチウムイオン二次電池は、単位電気量当たりの重量が小さく、エネルギー密度が高いため、急速に普及している。そのため、正極用材料であるリチウム遷移金属複合酸化物の開発が進められている。 In recent years, demand for non-aqueous electrolyte secondary batteries that are small and light and have a high energy density as a power source for portable devices and automobiles is rapidly increasing. Among them, a lithium ion secondary battery using a lithium transition metal composite oxide for a positive electrode is rapidly spreading because it has a small weight per unit quantity of electricity and a high energy density. Therefore, development of a lithium transition metal composite oxide, which is a positive electrode material, is underway.
一般に、リチウム遷移金属複合酸化物の製造方法は、リチウム含有物と遷移金属含有物とを混合して混合物を得る混合工程と、前記混合物を焼成容器に収容して焼成する焼成工程と、を備えている。 In general, a method for producing a lithium transition metal composite oxide includes a mixing step of mixing a lithium-containing material and a transition metal-containing material to obtain a mixture, and a baking step of storing the mixture in a baking container and baking the mixture. ing.
例えば特許文献１には、リチウム含有物と遷移金属含有物とを液体媒体中で粉砕し、これらを均一に分散させてスラリーを形成し、得られたスラリーを噴霧乾燥する噴霧乾燥工程と、得られた噴霧乾燥粉体を焼成する焼成工程とを備える、リチウム遷移金属複合酸化物の製造方法が記載されている。 For example, Patent Document 1 discloses a spray-drying process in which a lithium-containing material and a transition metal-containing material are pulverized in a liquid medium, uniformly dispersed to form a slurry, and the obtained slurry is spray-dried. A method for producing a lithium transition metal composite oxide comprising a firing step of firing the resulting spray-dried powder is described.
ところが、本発明者が正極用材料の開発を進めていく中で、層状岩塩構造のリチウム遷移金属複合酸化物を焼成容器に収容して焼成した際に、焼成後の焼成容器に析出物が生じ、再度焼成容器を用いてリチウム遷移金属複合酸化物を合成した際、組成ずれが生じる問題が生じた。一般に組成ずれが生じた場合には、容量の低下など、電池特性に様々な問題が生じる恐れがある。 However, when the present inventors are proceeding with the development of the positive electrode material, when a lithium transition metal composite oxide having a layered rock salt structure is placed in a firing container and fired, precipitates are generated in the fired firing container. When the lithium transition metal composite oxide was synthesized again using the firing container, there was a problem that composition deviation occurred. In general, when a compositional deviation occurs, various problems may occur in battery characteristics such as a decrease in capacity.
本発明は、上記の課題に鑑みなされたものであって、本発明は、組成ずれを防ぐことができる、リチウム遷移金属複合酸化物の製造方法を提供することを目的とする。 This invention is made | formed in view of said subject, Comprising: This invention aims at providing the manufacturing method of lithium transition metal complex oxide which can prevent a composition shift | offset | difference.
本発明者が実験したところ、リチウム遷移金属複合酸化物の焼成後の焼成容器を大気中に長時間放置すると、焼成容器の表面に析出物が現れることが分かった。そして、表面上に析出物が存在する焼成容器にリチウム含有物と遷移金属含有物の混合物を収容して焼成を行った場合に、混合物と析出物とが反応し、組成ずれが生じることを突き止めた。 As a result of experiments by the present inventors, it was found that when the firing container after firing the lithium transition metal composite oxide was left in the atmosphere for a long time, precipitates appeared on the surface of the firing container. Then, when a mixture of a lithium-containing material and a transition metal-containing material is contained in a firing container in which a precipitate is present on the surface and fired, the mixture and the precipitate are reacted to cause a compositional deviation. It was.
そこで、本発明者が鋭意研究したところ、焼成後の焼成容器を露点が１０℃以下の雰囲気下で保管することにより、析出物が現れないことを見出した。また、このような析出物の発生は層状岩塩構造に特有の現象であり、スピネル構造のリチウム遷移金属複合酸化物の場合には、析出物は発生しないことも分かった。 Then, when this inventor earnestly researched, it discovered that a deposit did not appear by storing the baking container after baking in the atmosphere whose dew point is 10 degrees C or less. It was also found that the generation of such a precipitate is a phenomenon peculiar to the layered rock salt structure, and no precipitate is generated in the case of a spinel structure lithium transition metal composite oxide.
本発明に係るリチウム遷移金属複合酸化物の製造方法は、リチウム含有物と遷移金属含有物とを混合して混合物を得る混合工程と、前記混合物を焼成容器に収容して焼成する焼成工程と、を備えるリチウム遷移金属複合酸化物の製造方法である。また、前記リチウム遷移金属複合酸化物は層状岩塩構造を有する。本発明において、前記焼成容器はセラミックを主成分として含有し、前記混合物を収容して一回以上焼成され、露点１０℃以下の雰囲気下で保管されたものであることを特徴としている。 The method for producing a lithium transition metal composite oxide according to the present invention comprises a mixing step of mixing a lithium-containing material and a transition metal-containing material to obtain a mixture, a firing step of containing the mixture in a firing container and firing. Is a method for producing a lithium transition metal composite oxide. The lithium transition metal composite oxide has a layered rock salt structure. In the present invention, the firing container contains ceramic as a main component, and contains the mixture, fired at least once, and stored in an atmosphere having a dew point of 10 ° C. or less.
本発明では、かかる構成により、リチウム遷移金属複合酸化物の焼成後の焼成容器に析出物の発生を防ぎ、焼成容器の繰り返しの使用から生ずる組成ずれを防ぐことができる。 In the present invention, with this configuration, it is possible to prevent the generation of precipitates in the firing container after firing the lithium transition metal composite oxide, and to prevent compositional deviation caused by repeated use of the firing container.
以下において、本発明を実施するための形態について説明する。 Hereinafter, modes for carrying out the present invention will be described.
本発明に係るリチウム遷移金属複合酸化物の製造方法は、混合工程と、焼成工程と、を備える。 The method for producing a lithium transition metal composite oxide according to the present invention includes a mixing step and a firing step.
まず、リチウム含有物と遷移金属含有物とを混合して混合物を得る混合工程を備える。リチウム含有物としては、リチウム金属単体や、炭酸リチウム、水酸化リチウム、硝酸リチウム、酸化リチウム、酢酸リチウム、水素化リチウム、硫酸リチウム、亜硝酸リチウム、ジカルボン酸リチウム、クエン酸リチウム、脂肪酸リチウム、アルキルリチウム、塩化リチウム、フッ素化リチウム、臭素化リチウム、ヨウ化リチウムなどのリチウムハロゲン化物等のリチウム化合物が挙げられる。遷移金属の例としては、マンガン、コバルト、ニッケルが挙げられる。また、これらを複数併用することができる。また、遷移金属含有物としては、遷移金属単体や遷移金属化合物が挙げられる。遷移金属化合物の例としては、酸化物、炭酸塩、無機酸塩、有機酸塩や塩化物等が挙げられる。 First, a mixing step of mixing a lithium-containing material and a transition metal-containing material to obtain a mixture is provided. Lithium-containing materials include lithium metal alone, lithium carbonate, lithium hydroxide, lithium nitrate, lithium oxide, lithium acetate, lithium hydride, lithium sulfate, lithium nitrite, lithium dicarboxylate, lithium citrate, fatty acid lithium, alkyl Examples of the lithium compound include lithium halides such as lithium, lithium chloride, lithium fluoride, lithium bromide, and lithium iodide. Examples of transition metals include manganese, cobalt, and nickel. A plurality of these can be used in combination. Examples of the transition metal-containing material include a transition metal simple substance and a transition metal compound. Examples of transition metal compounds include oxides, carbonates, inorganic acid salts, organic acid salts and chlorides.
混合の方法としては、例えばミルやミキサーによる混合が挙げられる。 Examples of the mixing method include mixing by a mill or a mixer.
本発明のリチウム遷移金属複合酸化物は、一般式ＬｉＡＯ2（Ａは遷移金属）で表される層状岩塩構造を有する。層状岩塩構造は、一般式ＬｉＡ2Ｏ4（Ａは遷移金属）で表されるスピネル構造に比べて、構造的に不安定である。したがって、焼成容器の表面に現れる析出物は、スピネル構造では現れず、層状岩塩構造のリチウム遷移金属複合酸化物に特有に現れる。 The lithium transition metal composite oxide of the present invention has a layered rock salt structure represented by the general formula LiAO 2 (A is a transition metal). The layered rock salt structure is structurally unstable compared to the spinel structure represented by the general formula LiA 2 O 4 (A is a transition metal). Therefore, the precipitate appearing on the surface of the firing container does not appear in the spinel structure, but appears specifically in the lithium transition metal composite oxide having a layered rock salt structure.
また、本発明のリチウム遷移金属複合酸化物は、Ｌｉ1+α（ＮｉxＭｎyＣｏz）Ｏ2（０≦α≦０．５、０≦ｘ≦１、０≦ｙ≦１、０≦ｚ≦１、ｘ＋ｙ＋ｚ＝１）の組成式を満足する場合に好適である。また、本発明のリチウム遷移金属複合酸化物は、少なくともＮｉとＣｏを含む場合に好適である。 Further, the lithium transition metal composite oxide of the present invention, Li 1+ α (Ni x Mn y Co z) O 2 (0 ≦ α ≦ 0.5,0 ≦ x ≦ 1,0 ≦ y ≦ 1,0 ≦ It is suitable when the composition formula of z ≦ 1, x + y + z = 1) is satisfied. The lithium transition metal composite oxide of the present invention is suitable when it contains at least Ni and Co.
次に、混合物を焼成容器に収容して焼成する工程を備える。焼成容器は、セラミックを主成分として含むことを特徴としている。セラミックとしては、Ａｌ2Ｏ3、ＳｉＯ2、ＺｒＯ2、ＭｇＯやこれらの混合物が挙げられる。また、Ａｌ2Ｏ3とＳｉＯ2を主成分として含む場合に好適である。さらに、リチウム遷移金属複合酸化物の焼成温度で安定な耐熱性セラミックである場合に好適である。また、本発明で用いられる焼成容器は、筒状、平板状、箱状など、形状に限定されない。 Next, the method includes a step of storing the mixture in a baking container and baking the mixture. The firing container is characterized by containing ceramic as a main component. Examples of the ceramic include Al 2 O 3 , SiO 2 , ZrO 2 , MgO, and a mixture thereof. Moreover, it is suitable when Al 2 O 3 and SiO 2 are contained as main components. Furthermore, it is suitable when the heat resistant ceramic is stable at the firing temperature of the lithium transition metal composite oxide. Moreover, the baking container used by this invention is not limited to shapes, such as a cylinder shape, flat plate shape, and box shape.
析出物は、一回以上混合物を収容して焼成している焼成容器に現れる。析出物は、下記のメカニズムで生じると考えられる。まず、焼成時にリチウムが酸化物となって焼成容器に吸収される。そして、そのリチウム酸化物がＨ2ＯやＣＯ2と反応し、Ｌｉ2ＣＯ3やＬｉＯＨ・Ｈ2Ｏ等のリチウム化合物となる。そしてその析出物が、時間と共に容器表面に析出してくると考えられる。したがって、焼成容器が金属製の場合には、そもそもリチウム酸化物が焼成容器に吸収されないため、かかる問題は生じない。 The precipitate appears in a firing container containing and firing the mixture one or more times. Precipitation is considered to occur by the following mechanism. First, during firing, lithium becomes an oxide and is absorbed by the firing container. Then, the lithium oxide reacts with H 2 O or CO 2 to become a lithium compound such as Li 2 CO 3 or LiOH · H 2 O. And it is thought that the deposit precipitates on the container surface with time. Therefore, when the firing container is made of metal, lithium oxide is not absorbed by the firing container in the first place, so that such a problem does not occur.
また、本発明の焼成温度は、６００℃以上１２００℃未満の範囲であることが好適である。７００℃以上１２００℃未満の範囲であることがより好適である。また、焼成容器を保管する際の露点の下限温度は０℃が好適である。 In addition, the firing temperature of the present invention is preferably in the range of 600 ° C. or more and less than 1200 ° C. It is more preferable that the temperature is in the range of 700 ° C or higher and lower than 1200 ° C. Moreover, 0 degreeC is suitable for the minimum temperature of the dew point at the time of storing a baking container.
ここで、組成や焼成条件の異なる混合物を同一の焼成容器を用いて焼成する場合には、焼成容器内の残留による混合を防ぐため、焼成後の焼成容器を水洗浄する場合がある。焼成容器を水洗浄した場合においても、水洗浄後に８０℃以上で焼成容器を加熱することで、析出物の発生を抑えて、組成ずれを防ぐことが可能となる。加熱の温度は、８０℃以上１５０℃以下が好適である。また、加熱時間は、６０分〜１８００分が好適である。すなわち、水洗浄後の焼成容器は８０℃以上で加熱された後、露点１０℃以下の雰囲気下で保管されることが好ましい。 Here, when baking the mixture from which a composition and baking conditions differ using the same baking container, in order to prevent the mixing by the residue in a baking container, the baking container after baking may be washed with water. Even when the firing container is washed with water, heating the firing container at 80 ° C. or higher after washing with water suppresses the generation of precipitates and prevents composition deviation. The heating temperature is preferably 80 ° C. or higher and 150 ° C. or lower. The heating time is preferably 60 minutes to 1800 minutes. That is, it is preferable that the baked container after water washing is stored at 80 ° C. or higher and then stored in an atmosphere with a dew point of 10 ° C. or lower.
（実験例１）
リチウム含有物としてＬｉ2ＣＯ3、遷移金属含有物として、金属ニッケル、Ｍｎ3Ｏ4、Ｃｏ3Ｏ4を使用した。そして、Ｌｉ：Ｎｉ：Ｍｎ：Ｃｏ＝１．０５：０．４５：０．４５：０．１０のモル比となるように秤量した。この秤量した原料を、
純水と混合し、スラリーを作製し、湿式混合を行った。次いで、噴霧乾燥して混合物を得た。その後、混合物をＡｌ2Ｏ3とＳｉＯ2を主成分とするセラミック製の焼成容器に収容して、焼成を行った。焼成は酸素雰囲気中で行った。焼成最高温度は９５０℃、焼成最高温度の保持時間は２０時間とした。昇温条件と降温条件はどちらも１５０℃／ｈとした。
(Experimental example 1)
Li 2 CO 3 was used as the lithium-containing material, and metallic nickel, Mn 3 O 4 , and Co 3 O 4 were used as the transition metal-containing material. And it weighed so that it might become a molar ratio of Li: Ni: Mn: Co = 1.05: 0.45: 0.45: 0.10. This weighed raw material
It was mixed with pure water to prepare a slurry, and wet mixing was performed. It was then spray dried to obtain a mixture. After that, the mixture was placed in a ceramic firing container mainly composed of Al 2 O 3 and SiO 2 and fired. Firing was performed in an oxygen atmosphere. The maximum firing temperature was 950 ° C., and the retention time of the maximum firing temperature was 20 hours. The temperature raising condition and the temperature lowering condition were both 150 ° C./h.
焼成後、焼成物を取り出した後に、水洗浄を行わずそのままの状態で焼成容器を露点０．５℃の条件下で４週間保管した。 After firing, after the fired product was taken out, the fired container was stored for 4 weeks under conditions of a dew point of 0.5 ° C. without washing with water.
４週間保管した焼成容器を用いて、再び同一組成のリチウム遷移金属複合酸化物の合成を行い、繰り返しの使用が可能かどうか検討した。 Using the firing container stored for 4 weeks, the lithium transition metal composite oxide having the same composition was synthesized again and examined whether it could be used repeatedly.
リチウム含有物としてＬｉ2ＣＯ3、遷移金属含有物として、金属ニッケル、Ｍｎ3Ｏ4、Ｃｏ3Ｏ4を使用した。そして、Ｌｉ：Ｎｉ：Ｍｎ：Ｃｏ＝１．０５：０．４５：０．４５：０．１０のモル比となるように秤量した。この秤量した原料を湿式混合した後、噴霧乾燥して混合物を得た。その後、４週間保管した焼成容器に収容して、焼成を行いリチウム遷移金属複合酸化物を合成した。リチウム遷移金属複合酸化物の組成分析を行ったところ、組成ずれは起こらなかった。 Li 2 CO 3 was used as the lithium-containing material, and metallic nickel, Mn 3 O 4 , and Co 3 O 4 were used as the transition metal-containing material. And it weighed so that it might become a molar ratio of Li: Ni: Mn: Co = 1.05: 0.45: 0.45: 0.10. The weighed raw materials were wet mixed and then spray dried to obtain a mixture. Then, it was housed in a firing container stored for 4 weeks and fired to synthesize a lithium transition metal composite oxide. Compositional analysis of the lithium transition metal composite oxide revealed no composition shift.
（実験例２）
実験例１と同じリチウム含有物と遷移金属含有物を用いて、Ｌｉ：Ｎｉ：Ｍｎ：Ｃｏ＝１．０５：０．３３：０．３３：０．３３のモル比となるように秤量した。そして、実験例１と同じ条件で混合物の焼成を行った。
(Experimental example 2)
Using the same lithium-containing material and transition metal-containing material as in Experimental Example 1, the materials were weighed so as to have a molar ratio of Li: Ni: Mn: Co = 1.05: 0.33: 0.33: 0.33. The mixture was fired under the same conditions as in Experimental Example 1.
焼成後、焼成物を取り出した後に、水洗浄を行わずそのままの状態で焼成容器を露点０．５℃の条件下で４週間保管した。 After firing, after the fired product was taken out, the fired container was stored for 4 weeks under conditions of a dew point of 0.5 ° C. without washing with water.
４週間保管した焼成容器を用いて、再びリチウム遷移金属複合酸化物の合成を行い、繰り返しの使用が可能かどうか検討した。組成分析の結果、組成ずれは起こらなかった。 Using the firing container stored for 4 weeks, the lithium transition metal composite oxide was synthesized again and examined whether it could be used repeatedly. As a result of the composition analysis, no composition shift occurred.
（実験例３）
実験例１と同じリチウム含有物と遷移金属含有物を用いて、Ｌｉ：Ｎｉ：Ｍｎ：Ｃｏ＝１．０５：０．８０：０．００：０．２０のモル比となるように秤量した。そして、実験例１と同じ条件で混合物の焼成を行った。
(Experimental example 3)
Using the same lithium-containing material and transition metal-containing material as in Experimental Example 1, the materials were weighed so as to have a molar ratio of Li: Ni: Mn: Co = 1.05: 0.80: 0.00: 0.20. The mixture was fired under the same conditions as in Experimental Example 1.
焼成後、焼成物を取り出した後に、水洗浄を行わずそのままの状態で焼成容器を露点０．５℃の条件下で４週間保管した。 After firing, after the fired product was taken out, the fired container was stored for 4 weeks under conditions of a dew point of 0.5 ° C. without washing with water.
４週間保管した焼成容器を用いて、再びリチウム遷移金属複合酸化物の合成を行い、繰り返しの使用が可能かどうか検討した。組成分析の結果、組成ずれは起こらなかった。 Using the firing container stored for 4 weeks, the lithium transition metal composite oxide was synthesized again and examined whether it could be used repeatedly. As a result of the composition analysis, no composition shift occurred.
（実験例４）
実験例１と同じリチウム含有物と遷移金属含有物を用いて、Ｌｉ：Ｎｉ：Ｍｎ：Ｃｏ＝１．０５：０．４５：０．４５：０．１０のモル比となるように秤量した。そして、実験例１と同じ条件で混合物の焼成を行った。
(Experimental example 4)
Using the same lithium-containing material and transition metal-containing material as in Experimental Example 1, the materials were weighed so as to have a molar ratio of Li: Ni: Mn: Co = 1.05: 0.45: 0.45: 0.10. The mixture was fired under the same conditions as in Experimental Example 1.
焼成後、焼成物を取り出した後に、水洗浄を行わずそのままの状態で焼成容器を露点１０．０℃の条件下で４週間保管した。 After firing, after the fired product was taken out, the fired container was stored for 4 weeks under the condition of a dew point of 10.0 ° C. without washing with water.
４週間保管した焼成容器を用いて、再びリチウム遷移金属複合酸化物の合成を行い、繰り返しの使用が可能かどうか検討した。組成分析の結果、組成ずれは起こらなかった。 Using the firing container stored for 4 weeks, the lithium transition metal composite oxide was synthesized again and examined whether it could be used repeatedly. As a result of the composition analysis, no composition shift occurred.
（実験例５）
実験例１と同じリチウム含有物と遷移金属含有物を用いて、Ｌｉ：Ｎｉ：Ｍｎ：Ｃｏ＝１．０５：０．４５：０．４５：０．１０のモル比となるように秤量した。そして、実験例１と同じ条件で混合物の焼成を行った。
(Experimental example 5)
Using the same lithium-containing material and transition metal-containing material as in Experimental Example 1, the materials were weighed so as to have a molar ratio of Li: Ni: Mn: Co = 1.05: 0.45: 0.45: 0.10. The mixture was fired under the same conditions as in Experimental Example 1.
焼成後、焼成物を取り出した後に、焼成容器の水洗を行った。その後、焼成容器を８０℃の条件で乾燥機で６００分間乾燥させた。その後、焼成容器を露点６．９℃の条件下で４週間保管した。 After firing, after the fired product was taken out, the firing container was washed with water. Then, the baking container was dried for 600 minutes with the dryer on 80 degreeC conditions. Thereafter, the baking container was stored for 4 weeks under conditions of a dew point of 6.9 ° C.
４週間保管した焼成容器を用いて、再びリチウム遷移金属複合酸化物の合成を行い、繰り返しの使用が可能かどうか検討した。組成分析の結果、組成ずれは起こらなかった。 Using the firing container stored for 4 weeks, the lithium transition metal composite oxide was synthesized again and examined whether it could be used repeatedly. As a result of the composition analysis, no composition shift occurred.
（比較例１）
実験例１と同じリチウム含有物と遷移金属含有物を用いて、Ｌｉ：Ｎｉ：Ｍｎ：Ｃｏ＝１．０５：０．４５：０．４５：０．１０のモル比となるように秤量した。そして、実験例１と同じ条件で混合物の焼成を行った。
(Comparative Example 1)
Using the same lithium-containing material and transition metal-containing material as in Experimental Example 1, the materials were weighed so as to have a molar ratio of Li: Ni: Mn: Co = 1.05: 0.45: 0.45: 0.10. The mixture was fired under the same conditions as in Experimental Example 1.
焼成後、焼成物を焼成容器から取り出した後に、水洗浄を行わずそのままの状態で焼成容器を露点１０．５℃の条件下で４週間保管した。 After firing, the fired product was taken out of the fired container, and then washed without water washing and stored for 4 weeks under the condition of a dew point of 10.5 ° C.
４週間保管した焼成容器を用いて、再びリチウム遷移金属複合酸化物の合成を行い、繰り返しの使用が可能かどうか検討した。組成分析の結果、組成ずれが発生した。 Using the firing container stored for 4 weeks, the lithium transition metal composite oxide was synthesized again and examined whether it could be used repeatedly. As a result of the composition analysis, compositional deviation occurred.
（比較例２）
実験例１と同じリチウム含有物と遷移金属含有物を用いて、組成がスピネル型であるリチウムマンガン複合酸化物ＬｉＭｎ2Ｏ4となるように秤量した。そして、実験例１と同じ条件で混合物の焼成を行った。
(Comparative Example 2)
Using the same lithium-containing material and transition metal-containing material as in Experimental Example 1, the lithium manganese composite oxide LiMn 2 O 4 having a spinel composition was weighed. The mixture was fired under the same conditions as in Experimental Example 1.
焼成後、焼成物を取り出した後に、水洗浄を行わずそのままの状態で焼成容器を露点１０．５℃の条件下で４週間保管した。 After firing, after the fired product was taken out, the fired container was stored for 4 weeks under the condition of a dew point of 10.5 ° C. without washing with water.
４週間保管した焼成容器を用いて、再びリチウム遷移金属複合酸化物の合成を行い、繰り返しの使用が可能かどうか検討した。組成分析の結果、組成ずれが発生した。 Using the firing container stored for 4 weeks, the lithium transition metal composite oxide was synthesized again and examined whether it could be used repeatedly. As a result of the composition analysis, compositional deviation occurred.
実験例１〜５と比較例１、２の保管後の焼成容器について、目視で外観を確認した。表１に４週間保管した後の焼成容器の析出物の有無と、焼成容器の繰り返し使用の可否を示す。リチウム遷移金属複合酸化物の２度目の合成後に組成ずれが起こらなかったものについて、繰り返し使用を○とした。そして、組成ずれが発生したものについて、繰り返し使用を×とした。 The appearances of the fired containers after storage in Experimental Examples 1 to 5 and Comparative Examples 1 and 2 were visually confirmed. Table 1 shows the presence or absence of deposits in the firing container after storage for 4 weeks, and whether or not the firing container can be used repeatedly. For the lithium transition metal composite oxide that did not undergo compositional deviation after the second synthesis, the repeated use was marked as ◯. And about the thing in which the composition shift | offset | difference generate | occur | produced, x was used repeatedly.
露点が１０℃以下である実験例１〜５については、析出物が発生しなかった。また、４週間保管後の焼成容器を再び用いてリチウム遷移金属複合酸化物を合成した際に、組成のずれなく焼成可能であった。ゆえに、繰り返し使用が可能である結果となった。実験例１〜３については、異なる組成であっても析出物の発生は抑えられている。また、水洗浄後に８０℃の温度で加熱した実験例５においても、析出物が発生しなかった。しかし、露点が１０．５℃である比較例１では保管後に析出物が発生した。また、４週間保管後の焼成容器を再び用いてリチウム遷移金属複合酸化物を合成した際、組成ずれが起こり、焼成容器を繰り返し使用できなかった。したがって、層状岩塩構造を有するリチウム遷移金属複合酸化物において、焼成容器の保管条件を露点１０℃以下とすることで、焼成容器を繰り返し使用することが可能となる。 In Experimental Examples 1 to 5 having a dew point of 10 ° C. or lower, no precipitate was generated. Further, when the lithium transition metal composite oxide was synthesized again using the firing container after storage for 4 weeks, it could be fired without deviation in composition. Therefore, the result was that it could be used repeatedly. About Experimental Examples 1-3, generation | occurrence | production of the precipitate is suppressed even if it is a different composition. Moreover, also in Experimental Example 5 heated at a temperature of 80 ° C. after washing with water, no precipitate was generated. However, in Comparative Example 1 having a dew point of 10.5 ° C., precipitates were generated after storage. Further, when the lithium transition metal composite oxide was synthesized again using the firing container stored for 4 weeks, the composition deviation occurred and the firing container could not be used repeatedly. Therefore, in the lithium transition metal composite oxide having a layered rock salt structure, the firing container can be used repeatedly by setting the storage condition of the firing container to a dew point of 10 ° C. or less.
また、比較例２は、スピネル構造の組成である。スピネル構造の場合には、露点が１０．５℃であっても、析出物は発生しなかった。 Comparative Example 2 has a spinel structure. In the case of the spinel structure, no precipitate was generated even when the dew point was 10.5 ° C.
図１に実験例１の保管後の焼成容器の写真を示す。また、図２に比較例１の保管後の焼成容器の写真を示す。実験例１では、保管後に析出物は発生していない。一方、比較例１では、焼成容器の底部に白い析出物を確認した。保管後に析出物が発生していることが分かる。 FIG. 1 shows a photograph of the firing container after storage in Experimental Example 1. Moreover, the photograph of the baking container after the storage of the comparative example 1 is shown in FIG. In Experimental Example 1, no precipitate was generated after storage. On the other hand, in Comparative Example 1, white precipitates were confirmed at the bottom of the firing container. It can be seen that precipitates are generated after storage.
Claims (2)
前記混合物を焼成容器に収容して焼成する焼成工程と、
を備えるリチウム遷移金属複合酸化物の製造方法において、
前記リチウム遷移金属複合酸化物は層状岩塩構造を有し、
前記焼成容器はセラミックを主成分として含有し、前記混合物を収容して一回以上焼成され、露点１０℃以下の雰囲気下で保管されたものであることを特徴とする、リチウム遷移金属複合酸化物の製造方法。 A mixing step of mixing a lithium-containing material and a transition metal-containing material to obtain a mixture;
A firing step of containing the mixture in a firing container and firing;
In a method for producing a lithium transition metal composite oxide comprising:
The lithium transition metal composite oxide has a layered rock salt structure,
Lithium transition metal composite oxide characterized in that the firing container contains ceramic as a main component, contains the mixture, is fired at least once, and is stored in an atmosphere having a dew point of 10 ° C. or less. Manufacturing method.
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