JP2020077475A - Method of producing cathode active material for all solid lithium ion battery and method of manufacturing all solid lithium ion battery - Google Patents

Method of producing cathode active material for all solid lithium ion battery and method of manufacturing all solid lithium ion battery Download PDF

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JP2020077475A
JP2020077475A JP2018208487A JP2018208487A JP2020077475A JP 2020077475 A JP2020077475 A JP 2020077475A JP 2018208487 A JP2018208487 A JP 2018208487A JP 2018208487 A JP2018208487 A JP 2018208487A JP 2020077475 A JP2020077475 A JP 2020077475A
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JP7292026B2 (en
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幸毅 ▲柳▼川
幸毅 ▲柳▼川
Yukitake Yanagawa
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JX Nippon Mining and Metals Corp
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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
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Abstract

To provide a method of producing cathode active material for an all solid lithium ion battery having an excellent battery characteristic.SOLUTION: The method of producing cathode active material for an all solid lithium ion battery is provided that includes the steps of: preparing a transition-metal compound constituted by nickel, cobalt, and manganese; adding a gallium compound to the transition-metal compound thereby obtaining a transition-metal compound added with gallium compound expressed by a composition formula: NiCoMnGa(in the formula, 84<a<94, 5<b<7.5, 1≤c<7.5, and 0.33≤d≤0.65); mixing the transition-metal compound added with gallium compound and a lithium hydroxide thereby obtaining a mixture; and performing a heat treatment on the mixture.SELECTED DRAWING: None

Description

本発明は、全固体リチウムイオン電池用正極活物質の製造方法、及び、全固体リチウムイオン電池の製造方法に関する。   The present invention relates to a method for producing a positive electrode active material for an all-solid-state lithium-ion battery and a method for producing an all-solid-state lithium-ion battery.

現在、使用されているリチウムイオン電池は、正極活物質として層状化合物ＬｉＭｅＯ2（Ｍｅは平均で＋ＩＩＩ価となるように選択されるカチオンであり、レドックスカチオンを必ず含む)、スピネル化合物ＬｉＭｅＱＯ4（Ｑは平均で＋ＩＶ価となるように選択されるカチオン)、オリビン系化合物ＬｉＸ１Ｘ２Ｏ4（Ｘ１は＋ＩＩ価となるように選択されるカチオンであり、レドックスカチオンを必ず含む、Ｘ２は＋Ｖ価となるように選択されるカチオン)や蛍石型化合物Ｌｉ5ＭｅＯ4等を用いており、一方でその特性を生かすことができるよう、電解液その他構成要件が年々改善されてきている。 Currently used lithium ion batteries include a layered compound LiMeO 2 (Me is a cation selected so as to have an average + III valence and always includes a redox cation) as a positive electrode active material, and a spinel compound LiMeQO 4 (Q Is a cation selected to have an average + IV valence), and an olivine compound LiX1X2O 4 (X1 is a cation selected to have a + II valence, and must include a redox cation, and X2 has a + V valence). (Selected cations) and fluorite type compounds Li 5 MeO 4 and the like are used, and on the other hand, the electrolytic solution and other constituent requirements have been improved year by year so that the characteristics can be utilized.

ただ、リチウムイオン電池の場合は、電解液は有機化合物が大半であり、たとえ難燃性の化合物を用いたとしても火災に至る危険性が全くなくなるとは言いきれない。こうした液系リチウムイオン電池（以下、液系ＬＩＢとも称する）の代替候補として、電解質を固体とした全固体リチウムイオン電池（以下、全固体ＬＩＢとも称する）が近年注目を集めている（特許文献１等）。   However, in the case of a lithium-ion battery, most electrolytes are organic compounds, and it cannot be said that even if a flame-retardant compound is used, there is no danger of causing a fire. As an alternative candidate for such a liquid-type lithium-ion battery (hereinafter, also referred to as a liquid-type LIB), an all-solid-state lithium-ion battery having an electrolyte as a solid (hereinafter also referred to as an all-solid-state LIB) has been attracting attention in recent years (Patent Document 1). etc).

特許第５９７１１０９号公報Japanese Patent No. 5971109 特許第５２４６７７７号公報Japanese Patent No. 5246777

しかしながら、充放電中の発熱による電池性能の劣化抑制は全固体ＬＩＢにも共通の課題として、改善が求められている。   However, suppression of deterioration of battery performance due to heat generation during charging / discharging is a common problem for all solid-state LIBs, and improvement is required.

ここで、正極活物質を得るためには、特許文献２にも開示されている通り、前駆体とリチウム源とを混合、焼成し正極活物質を得るのが一般的であるが、このような製造方法では正極活物質合成中でのリチウムイオン拡散のために大きなエネルギーを必要とする。このため、従来技術では、実験例のスケールアップの際に想定性能が発揮できないことがあった。具体的には、上記のリチウムイオン拡散が不十分であることから、未反応分が残ってしまい、結果として残存した未反応原料の一部が充放電時に反応抵抗(リチウムイオン拡散抵抗)となってしまってジュール熱が発生し、出力特性やサイクル特性などにまで悪影響を及ぼしてしまうということがあった。   Here, in order to obtain the positive electrode active material, as disclosed in Patent Document 2, it is common to mix a precursor and a lithium source and fire the mixture to obtain a positive electrode active material. The manufacturing method requires a large amount of energy for diffusion of lithium ions during the synthesis of the positive electrode active material. For this reason, in the related art, the expected performance may not be exhibited when the experimental example is scaled up. Specifically, since the above lithium ion diffusion is insufficient, unreacted components remain, and as a result, some of the unreacted raw materials that remain become reaction resistance (lithium ion diffusion resistance) during charge and discharge. As a result, Joule heat is generated, which adversely affects output characteristics and cycle characteristics.

そこで、本発明の実施形態は、電池特性が良好な全固体リチウムイオン電池用正極活物質の製造方法を提供することを課題とする。   Therefore, it is an object of an embodiment of the present invention to provide a method for producing a positive electrode active material for an all-solid-state lithium-ion battery having good battery characteristics.

本発明は一実施形態において、ニッケル、コバルト及びマンガンで構成される遷移金属化合物を準備する工程と、前記遷移金属化合物にガリウム化合物を添加して、組成式：ＮｉaＣｏbＭｎcＧａd（式中、８４＜ａ＜９４、５＜ｂ＜７．５、１≦ｃ＜７．５、０．３３≦ｄ≦０．６５である）で表されるガリウム添加遷移金属化合物を得る工程と、前記ガリウム添加遷移金属化合物と水酸化リチウムとを混合して混合体を得る工程と、前記混合体を熱処理する工程とを含む全固体リチウムイオン電池用正極活物質の製造方法である。 In one embodiment, the present invention provides a step of preparing a transition metal compound composed of nickel, cobalt, and manganese, and adding a gallium compound to the transition metal compound to obtain a composition formula: Ni a Co b M n c Ga d ( In the formula, 84 <a <94, 5 <b <7.5, 1 ≦ c <7.5, 0.33 ≦ d ≦ 0.65). A method for producing a positive electrode active material for an all-solid-state lithium-ion battery, comprising: a step of mixing the gallium-added transition metal compound and lithium hydroxide to obtain a mixture; and a step of heat-treating the mixture.

本発明の別の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法は、前記ニッケル、コバルト及びマンガンで構成される遷移金属化合物が水酸化物である。   In the method for producing a positive electrode active material for an all-solid-state lithium-ion battery according to another embodiment of the present invention, the transition metal compound composed of nickel, cobalt and manganese is a hydroxide.

本発明の更に別の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法は、前記遷移金属化合物に添加するガリウム化合物がクエン酸ガリウムである。   In the method for producing a positive electrode active material for an all-solid-state lithium ion battery according to yet another embodiment of the present invention, the gallium compound added to the transition metal compound is gallium citrate.

本発明の別の実施形態は、本発明の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法によって製造された全固体リチウムイオン電池用正極活物質を用いて正極層を形成し、前記正極層、固体電解質層及び負極層を用いて全固体リチウムイオン電池を製造する全固体リチウムイオン電池の製造方法である。   Another embodiment of the present invention is to form a positive electrode layer using the all-solid-state lithium-ion battery positive electrode active material manufactured by the method for manufacturing an all-solid-state lithium-ion battery positive electrode active material according to the embodiment of the present invention, An all-solid-state lithium-ion battery is manufactured by using the positive electrode layer, the solid electrolyte layer, and the negative electrode layer.

本発明の実施形態によれば、電池特性が良好な全固体リチウムイオン電池用正極活物質の製造方法を提供することができる。   According to the embodiments of the present invention, it is possible to provide a method for producing a positive electrode active material for an all-solid-state lithium-ion battery having good battery characteristics.

（全固体リチウムイオン電池用正極活物質の製造方法）
本発明の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法としては、まず、ニッケル、コバルト及びマンガンで構成される遷移金属化合物を準備する。遷移金属化合物はニッケル源：コバルト源：マンガン源が、所定のモル比となるように調製されている。ニッケル源、コバルト源、マンガン源はそれぞれ硫酸塩、硝酸塩、酢酸塩等から選択される少なくとも１種の組み合わせであってもよい。また、当該遷移金属化合物は水酸化物、酸化物等であってもよい。 (Method for producing positive electrode active material for all-solid-state lithium-ion battery)
In the method for producing the positive electrode active material for an all-solid-state lithium ion battery according to the embodiment of the present invention, first, a transition metal compound composed of nickel, cobalt and manganese is prepared. The transition metal compound is prepared such that a nickel source: cobalt source: manganese source has a predetermined molar ratio. The nickel source, cobalt source, and manganese source may each be a combination of at least one selected from sulfates, nitrates, acetates, and the like. Further, the transition metal compound may be a hydroxide, an oxide or the like.

次に、ニッケル、コバルト及びマンガンで構成される遷移金属化合物にガリウム化合物を添加して、組成式：ＮｉaＣｏbＭｎcＧａd（式中、８４＜ａ＜９４、５＜ｂ＜７．５、１≦ｃ＜７．５、０．３３≦ｄ≦０．６５である）で表されるガリウム添加遷移金属化合物を作製する。当該遷移金属化合物に添加するガリウム化合物は、クエン酸ガリウム、硝酸ガリウム等であってもよい。Ｇａの組成について、上記組成式においてｄが０．３３以下であると、ガリウム添加によるリチウムイオンの拡散抵抗低減効果が十分に得られないという問題が生じるおそれがあり、ｄが０．６５以上であると電荷のキャリアであるリチウムイオンが本来存在する場所を奪い放電容量が低下するという問題が生じるおそれがある。 Next, a gallium compound is added to a transition metal compound composed of nickel, cobalt, and manganese, and a composition formula: Ni a Co b Mn c Ga d (wherein 84 <a <94, 5 <b <7. 5, 1 ≦ c <7.5, 0.33 ≦ d ≦ 0.65) is prepared. The gallium compound added to the transition metal compound may be gallium citrate, gallium nitrate, or the like. Regarding the composition of Ga, when d is 0.33 or less in the above composition formula, there is a possibility that the effect of reducing the diffusion resistance of lithium ions due to the addition of gallium may not be sufficiently obtained, and d is 0.65 or more. If so, there is a possibility that a problem may occur in which the place where the lithium ion, which is a carrier of electric charge, originally exists is deprived to lower the discharge capacity.

ニッケル、コバルト及びマンガンで構成される遷移金属化合物にガリウム化合物を添加してガリウム添加遷移金属化合物を作製する方法としては、特に限定されないが、例えば当該遷移金属化合物にロッキングミキサー等で所定のＧａ濃度のガリウム化合物の溶液を噴霧して撹拌することでガリウム添加遷移金属化合物を作製する方法等が挙げられる。   The method of adding a gallium compound to a transition metal compound composed of nickel, cobalt, and manganese to produce a gallium-added transition metal compound is not particularly limited, but, for example, the transition metal compound may have a predetermined Ga concentration by a rocking mixer or the like. And a method of producing a gallium-added transition metal compound by spraying and stirring a solution of the gallium compound.

次に、ガリウム添加遷移金属化合物と水酸化リチウムとを混合して混合体を得る。混合は特に限定されないが、例えばヘンシェルミキサー等を用いて行うことができる。   Next, a gallium-added transition metal compound and lithium hydroxide are mixed to obtain a mixture. The mixing is not particularly limited, but can be performed using, for example, a Henschel mixer.

次に、混合体を熱処理する。当該熱処理としては、好ましくは酸素雰囲気下で、７００℃で１２時間の焼成を行うことができる。焼成後、所定の降温速度で室温まで冷却し、必要であれば、ロールクラッシャーやパルベライザー等で解砕することで、本発明の実施形態に係る全固体リチウムイオン電池用正極活物質が得られる。   Next, the mixture is heat-treated. As the heat treatment, firing can be performed at 700 ° C. for 12 hours, preferably in an oxygen atmosphere. After firing, the positive electrode active material for an all-solid-state lithium ion battery according to the embodiment of the present invention is obtained by cooling to room temperature at a predetermined temperature lowering rate and, if necessary, crushing with a roll crusher, a pulsarizer or the like.

上記の方法によれば、正極活物質前駆体にリチウムとイオン半径の近いガリウムを添加してガリウム添加遷移金属化合物を作製し、これをリチウム源と混合して焼成することで、焼成中および充放電中のリチウムの拡散をしやすくし、電池の抵抗を減少させ、抵抗ジュール熱起因の発熱を抑制し、結果として全固体リチウムイオン電池の電池特性を向上させる正極活物質が得られる。これは、添加されたガリウムによって、正極活物質前駆体の構造が周期的に変動し、結果としてリチウムイオンの吸着エネルギーも変動し、これにより、焼成中および充放電中のリチウムの拡散が容易になるためと考えられる。   According to the above method, gallium having a ionic radius close to that of lithium is added to the positive electrode active material precursor to prepare a gallium-added transition metal compound, which is mixed with a lithium source and then baked, so that during and after firing. A positive electrode active material that facilitates diffusion of lithium during discharge, reduces the resistance of the battery, suppresses heat generation due to resistance Joule heat, and consequently improves the battery characteristics of an all-solid-state lithium-ion battery is obtained. This is because the structure of the positive electrode active material precursor is periodically changed by the added gallium, and as a result, the adsorption energy of lithium ions is also changed, which facilitates the diffusion of lithium during firing and charging / discharging. It is thought to be because.

（全固体リチウムイオン電池の製造方法）
本発明の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法によって製造された全固体リチウムイオン電池用正極活物質を用いて正極層を形成し、固体電解質層、当該正極層及び負極層を備えた全固体リチウムイオン電池を作製することができる。 (Method for manufacturing all-solid-state lithium-ion battery)
A positive electrode layer is formed using the positive electrode active material for all-solid-state lithium-ion batteries manufactured by the method for manufacturing a positive-electrode active material for all-solid-state lithium-ion batteries according to an embodiment of the present invention, and a solid electrolyte layer, the positive-electrode layer and the negative electrode. An all-solid-state lithium-ion battery with layers can be made.

以下、本発明及びその利点をより良く理解するための実施例を提供するが、本発明はこれらの実施例に限られるものではない。   Examples are provided below for better understanding of the present invention and its advantages, but the present invention is not limited to these examples.

（実施例１）
正極活物質前駆体であるニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物（モル比でＮｉ：Ｃｏ：Ｍｎ＝８９．９：６．８９：２．８９）に対し、室温にてロッキングミキサーを用いて、表１に示すＧａ添加条件にてＧａ濃度７．０質量％のクエン酸ガリウム溶液を噴霧し、１５分間粉体撹拌を実施し、ガリウム添加遷移金属の水酸化物（ガリウム添加前駆体）Ａを得た。ここで、該クエン酸ガリウム溶液の噴霧は、該遷移金属の水酸化物中のＮｉ＋Ｃｏ＋Ｍｎの総モルに対する、噴霧したクエン酸ガリウム溶液中のＧａのモル数の割合：Ｇａ／（Ｎｉ＋Ｃｏ＋Ｍｎ）が０．３３ｍｏｌ％となるように行った。また、得られたガリウム添加前駆体の平均粒径Ｄ５０は１３μｍであり、比表面積（ＢＥＴ）は２５ｍ2／ｇであった。
次に、該ガリウム添加前駆体Ａと水酸化リチウムとをヘンシェルミキサーを用いて１５００ｒｐｍで５分間混合した。混合して得られた粉体を０．１Ｍｐａ酸素雰囲気下、７２０℃で１２時間焼成した。これを降温速度５℃／分で室温まで冷却し、ロールクラッシャーとＡＣＭパルベライザーで解砕して全固体リチウムイオン電池用正極活物質Ａを得た。 (Example 1)
The positive electrode active material precursor is a transition metal hydroxide composed of nickel, cobalt and manganese (at a molar ratio of Ni: Co: Mn = 89.9: 6.89: 2.89) at room temperature. Using a rocking mixer, a gallium citrate solution having a Ga concentration of 7.0 mass% was sprayed under the Ga addition conditions shown in Table 1, and powder stirring was carried out for 15 minutes to obtain a hydroxide of gallium-added transition metal (gallium. Addition precursor) A was obtained. Here, in the spraying of the gallium citrate solution, the ratio of the number of moles of Ga in the sprayed gallium citrate solution to the total moles of Ni + Co + Mn in the hydroxide of the transition metal: Ga / (Ni + Co + Mn) was 0. It carried out so that it might be 33 mol%. The average particle diameter D50 of the obtained gallium-containing precursor was 13 μm, and the specific surface area (BET) was 25 m 2 / g.
Next, the gallium-added precursor A and lithium hydroxide were mixed with a Henschel mixer at 1500 rpm for 5 minutes. The powder obtained by mixing was fired at 720 ° C. for 12 hours in an oxygen atmosphere of 0.1 Mpa. This was cooled to room temperature at a temperature decrease rate of 5 ° C./min, and crushed with a roll crusher and an ACM pulsarizer to obtain a positive electrode active material A for all-solid-state lithium ion batteries.

（実施例２）
正極活物質前駆体であるニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物（モル比でＮｉ：Ｃｏ：Ｍｎ＝８４．８：７．３４：７．３４）に対し、室温にてロッキングミキサーを用いて、表１に示すＧａ添加条件にてＧａ濃度７．０質量％のクエン酸ガリウム溶液を噴霧し、１５分間粉体撹拌を実施し、ガリウム添加遷移金属の水酸化物（ガリウム添加前駆体）Ｂを得た。ここで、該クエン酸ガリウム溶液の噴霧は、該遷移金属の水酸化物中のＮｉ＋Ｃｏ＋Ｍｎの総モルに対する、噴霧したクエン酸ガリウム溶液中のＧａのモル数の割合：Ｇａ／（Ｎｉ＋Ｃｏ＋Ｍｎ）が０．４８ｍｏｌ％となるように行った。また、得られたガリウム添加前駆体の平均粒径Ｄ５０は１０μｍであり、比表面積（ＢＥＴ）は４０ｍ2／ｇであった。
次に、該ガリウム添加前駆体Ｂと水酸化リチウムとをヘンシェルミキサーを用いて１５００ｒｐｍで５分間混合した。混合して得られた粉体を０．１Ｍｐａ酸素雰囲気下、７２０℃で１２時間焼成した。これを降温速度５℃／分で室温まで冷却し、ロールクラッシャーとＡＣＭパルベライザーで解砕して全固体リチウムイオン電池用正極活物質Ｂを得た。 (Example 2)
The positive electrode active material precursor is a transition metal hydroxide composed of nickel, cobalt and manganese (at a molar ratio of Ni: Co: Mn = 84.8: 7.34: 7.34) at room temperature. Using a rocking mixer, a gallium citrate solution having a Ga concentration of 7.0 mass% was sprayed under the Ga addition conditions shown in Table 1, and powder stirring was carried out for 15 minutes to obtain a hydroxide of gallium-added transition metal (gallium. Added precursor B was obtained. Here, in the spraying of the gallium citrate solution, the ratio of the number of moles of Ga in the sprayed gallium citrate solution to the total moles of Ni + Co + Mn in the hydroxide of the transition metal: Ga / (Ni + Co + Mn) was 0. It was carried out so as to be 48 mol%. The average particle diameter D50 of the obtained gallium-containing precursor was 10 μm, and the specific surface area (BET) was 40 m 2 / g.
Next, the gallium-added precursor B and lithium hydroxide were mixed for 5 minutes at 1500 rpm using a Henschel mixer. The powder obtained by mixing was fired at 720 ° C. for 12 hours in an oxygen atmosphere of 0.1 Mpa. This was cooled to room temperature at a temperature decrease rate of 5 ° C./min, and crushed with a roll crusher and an ACM pulsarizer to obtain a positive electrode active material B for all-solid-state lithium ion battery.

（実施例３）
正極活物質前駆体であるニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物（モル比でＮｉ：Ｃｏ：Ｍｎ＝９３．３：５．１：１）に対し、室温にてロッキングミキサーを用いて、表１に示すＧａ添加条件にてＧａ濃度７．０質量％のクエン酸ガリウム溶液を噴霧し、１５分間粉体撹拌を実施し、ガリウム添加遷移金属の水酸化物（ガリウム添加前駆体）Ｃを得た。ここで、該クエン酸ガリウム溶液の噴霧は、該遷移金属の水酸化物中のＮｉ＋Ｃｏ＋Ｍｎの総モルに対する、噴霧したクエン酸ガリウム溶液中のＧａのモル数の割合：Ｇａ／（Ｎｉ＋Ｃｏ＋Ｍｎ）が０．６５ｍｏｌ％となるように行った。また、得られたガリウム添加前駆体の平均粒径Ｄ５０は８μｍであり、比表面積（ＢＥＴ）は３０ｍ2／ｇであった。
次に、該ガリウム添加前駆体Ｃと水酸化リチウムとをヘンシェルミキサーを用いて１５００ｒｐｍで５分間混合した。混合して得られた粉体を０．１Ｍｐａ酸素雰囲気下、７２０℃で１２時間焼成した。これを降温速度５℃／分で室温まで冷却し、ロールクラッシャーとＡＣＭパルベライザーで解砕して全固体リチウムイオン電池用正極活物質Ｃを得た。 (Example 3)
Rocking mixer at room temperature for a hydroxide of a transition metal composed of nickel, cobalt and manganese (a molar ratio of Ni: Co: Mn = 93.3: 5.1: 1) which is a positive electrode active material precursor. By spraying a gallium citrate solution having a Ga concentration of 7.0% by mass under the Ga addition conditions shown in Table 1 and performing powder agitation for 15 minutes. Body C was obtained. Here, in the spraying of the gallium citrate solution, the ratio of the number of moles of Ga in the sprayed gallium citrate solution to the total moles of Ni + Co + Mn in the hydroxide of the transition metal: Ga / (Ni + Co + Mn) was 0. It carried out so that it might become 65 mol%. The average particle size D50 of the obtained gallium-containing precursor was 8 μm, and the specific surface area (BET) was 30 m 2 / g.
Next, the gallium-added precursor C and lithium hydroxide were mixed for 5 minutes at 1500 rpm using a Henschel mixer. The powder obtained by mixing was fired at 720 ° C. for 12 hours in an oxygen atmosphere of 0.1 Mpa. This was cooled to room temperature at a temperature decrease rate of 5 ° C./min, and crushed with a roll crusher and an ACM pulsarizer to obtain a positive electrode active material C for an all-solid-state lithium ion battery.

（比較例１）
正極活物質前駆体であるニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物（モル比でＮｉ：Ｃｏ：Ｍｎ＝９４：４．９：０．９）に対し、室温にてロッキングミキサーを用いて、表１に示すＧａ添加条件にてＧａ濃度７．０質量％のクエン酸ガリウム溶液を噴霧し、１５分間粉体撹拌を実施し、ガリウム添加遷移金属の水酸化物（ガリウム添加前駆体）Ｄを得た。ここで、該クエン酸ガリウム溶液の噴霧は、該遷移金属の水酸化物中のＮｉ＋Ｃｏ＋Ｍｎの総モルに対する、噴霧したクエン酸ガリウム溶液中のＧａのモル数の割合：Ｇａ／（Ｎｉ＋Ｃｏ＋Ｍｎ）が０．１６ｍｏｌ％となるように行った。また、得られたガリウム添加前駆体の平均粒径Ｄ５０は８μｍであり、比表面積（ＢＥＴ）は３０ｍ2／ｇであった。
次に、該ガリウム添加前駆体Ｄと水酸化リチウムとをヘンシェルミキサーを用いて１５００ｒｐｍで５分間混合した。混合して得られた粉体を０．１Ｍｐａ酸素雰囲気下、７２０℃で１２時間焼成した。これを降温速度５℃／分で室温まで冷却し、ロールクラッシャーとＡＣＭパルベライザーで解砕して全固体リチウムイオン電池用正極活物質Ｄを得た。 (Comparative Example 1)
Rocking mixer at room temperature for a transition metal hydroxide (Ni: Co: Mn = 94: 4.9: 0.9 in molar ratio) composed of nickel, cobalt, and manganese, which is a positive electrode active material precursor. By spraying a gallium citrate solution having a Ga concentration of 7.0 mass% under the Ga addition conditions shown in Table 1 and performing powder agitation for 15 minutes to prepare a gallium-added transition metal hydroxide (gallium-added precursor). Body) D was obtained. Here, in the spraying of the gallium citrate solution, the ratio of the number of moles of Ga in the sprayed gallium citrate solution to the total moles of Ni + Co + Mn in the hydroxide of the transition metal: Ga / (Ni + Co + Mn) was 0. It carried out so that it might be 16 mol%. The average particle size D50 of the obtained gallium-containing precursor was 8 μm, and the specific surface area (BET) was 30 m 2 / g.
Next, the gallium-added precursor D and lithium hydroxide were mixed at 1500 rpm for 5 minutes using a Henschel mixer. The powder obtained by mixing was fired at 720 ° C. for 12 hours in an oxygen atmosphere of 0.1 Mpa. This was cooled to room temperature at a temperature lowering rate of 5 ° C./min, and crushed with a roll crusher and an ACM pulsarizer to obtain a positive electrode active material D for all-solid-state lithium ion battery.

（比較例２）
正極活物質前駆体であるニッケル、コバルト及びマンガンで構成される遷移金属の水酸化物（モル比でＮｉ：Ｃｏ：Ｍｎ＝８３．９：７．７：７．７）に対し、室温にてロッキングミキサーを用いて、表１に示すＧａ添加条件にてＧａ濃度７．０質量％のクエン酸ガリウム溶液を噴霧し、１５分間粉体撹拌を実施し、ガリウム添加遷移金属の水酸化物（ガリウム添加前駆体）Ｅを得た。ここで、該クエン酸ガリウム溶液の噴霧は、該遷移金属の水酸化物中のＮｉ＋Ｃｏ＋Ｍｎの総モルに対する、噴霧したクエン酸ガリウム溶液中のＧａのモル数の割合：Ｇａ／（Ｎｉ＋Ｃｏ＋Ｍｎ）が０．７５ｍｏｌ％となるように行った。また、得られたガリウム添加前駆体の平均粒径Ｄ５０は１０μｍであり、比表面積（ＢＥＴ）は４０ｍ2／ｇであった。
次に、該ガリウム添加前駆体Ｅと水酸化リチウムとをヘンシェルミキサーを用いて１５００ｒｐｍで５分間混合した。混合して得られた粉体を０．１Ｍｐａ酸素雰囲気下、７２０℃で１２時間焼成した。これを降温速度５℃／分で室温まで冷却し、ロールクラッシャーとＡＣＭパルベライザーで解砕して全固体リチウムイオン電池用正極活物質Ｅを得た。 (Comparative example 2)
For a positive electrode active material precursor, a transition metal hydroxide composed of nickel, cobalt and manganese (Ni: Co: Mn = 83.9: 7.7: 7.7 in a molar ratio), at room temperature. Using a rocking mixer, a gallium citrate solution having a Ga concentration of 7.0 mass% was sprayed under the Ga addition conditions shown in Table 1, and powder stirring was carried out for 15 minutes to obtain a hydroxide of gallium-added transition metal (gallium. Addition precursor) E was obtained. Here, in the spraying of the gallium citrate solution, the ratio of the number of moles of Ga in the sprayed gallium citrate solution to the total moles of Ni + Co + Mn in the hydroxide of the transition metal: Ga / (Ni + Co + Mn) was 0. It was performed so as to be 75 mol%. The average particle diameter D50 of the obtained gallium-containing precursor was 10 μm, and the specific surface area (BET) was 40 m 2 / g.
Next, the gallium-added precursor E and lithium hydroxide were mixed with a Henschel mixer at 1500 rpm for 5 minutes. The powder obtained by mixing was fired at 720 ° C. for 12 hours in an oxygen atmosphere of 0.1 Mpa. This was cooled to room temperature at a temperature lowering rate of 5 ° C./min, and crushed with a roll crusher and an ACM pulsarizer to obtain a positive electrode active material E for all-solid-state lithium ion batteries.

−電池特性の評価（全固体リチウムイオン電池）−
得られた正極活物質Ａ〜Ｅについて、それぞれＬｉＩ−Ｌｉ2Ｓ−Ｐ2Ｓ5と、正極活物質の重量：ＬｉＩ−Ｌｉ2Ｓ−Ｐ2Ｓ5の重量＝７：３の割合で秤量し、混合して正極合剤とした。内径１０ｍｍの金型中にＬｉ−Ｉｎ合金、ＬｉＩ−Ｌｉ2Ｓ−Ｐ2Ｓ5、正極合剤、Ａｌ箔をこの順で充填し、５００ＭＰａでプレスした。このプレス後の成形体を、金属製治具を用いて１００ＭＰａで拘束することにより、全固体リチウムイオン電池を作製した。この電池について、充放電レート１Ｃで充放電を１０回繰り返した（２５℃、充電上限電圧：３．７Ｖ、放電下限電圧：２．５Ｖ）。充放電レート１Ｃでの１回目の放電で得られた容量を放電容量２とし、また、充放電レート１Ｃでの１０回目の放電で得られた容量を放電容量３とし、（放電容量３）／（放電容量２）の比を百分率としてサイクル特性（％）とした。得られた結果を表１に示す。 -Evaluation of battery characteristics (all-solid-state lithium-ion battery)-
The obtained positive electrode active material A-E, respectively LiI-Li 2 S-P 2 S 5, the weight of the positive electrode active material: LiI-Li 2 S-P 2 S 5 Weight = 7: weighed at a ratio of 3 Then, they were mixed to obtain a positive electrode mixture. Li-an In alloy into a mold having an inner diameter of 10mm, LiI-Li 2 S- P 2 S 5, the positive electrode mixture, filling the Al foil in this order, and pressed at 500 MPa. The all-solid-state lithium-ion battery was manufactured by restraining the pressed body at 100 MPa using a metal jig. This battery was repeatedly charged and discharged 10 times at a charge and discharge rate of 1 C (25 ° C., charge upper limit voltage: 3.7 V, discharge lower limit voltage: 2.5 V). The capacity obtained by the first discharge at a charge / discharge rate of 1C is defined as a discharge capacity 2, and the capacity obtained by the 10th discharge at a charge / discharge rate of 1C is defined as a discharge capacity 3, (discharge capacity 3) / The ratio of (discharge capacity 2) was taken as a percentage and used as the cycle characteristic (%). The results obtained are shown in Table 1.

Figure 2020077475
Figure 2020077475

（評価結果）
実施例１〜３では電池特性が良好な全固体リチウムイオン電池用正極活物質が得られた。一方、比較例１、比較例２は遷水酸化リチウムと混合する遷移金属化合物にＧａが添加されておらず、全固体リチウムイオン電池用正極活物質の電池特性は実施例１〜３に対して劣っていた。 (Evaluation results)
In Examples 1 to 3, positive electrode active materials for all-solid-state lithium ion batteries having good battery characteristics were obtained. On the other hand, in Comparative Example 1 and Comparative Example 2, Ga is not added to the transition metal compound mixed with lithium transition hydroxide, and the battery characteristics of the positive electrode active material for all-solid-state lithium-ion batteries are the same as those of Examples 1 to 3. It was inferior.

Claims (4)

ニッケル、コバルト及びマンガンで構成される遷移金属化合物を準備する工程と、
前記遷移金属化合物にガリウム化合物を添加して、組成式：ＮｉaＣｏbＭｎcＧａd
（式中、８４＜ａ＜９４、５＜ｂ＜７．５、１≦ｃ＜７．５、０．３３≦ｄ≦０．６５である）
で表されるガリウム添加遷移金属化合物を得る工程と、
前記ガリウム添加遷移金属化合物と水酸化リチウムとを混合して混合体を得る工程と、
前記混合体を熱処理する工程と、
を含む全固体リチウムイオン電池用正極活物質の製造方法。 Providing a transition metal compound composed of nickel, cobalt and manganese,
A gallium compound is added to the transition metal compound to give a composition formula: Ni a Co b Mn c Ga d.
(In the formula, 84 <a <94, 5 <b <7.5, 1 ≦ c <7.5, 0.33 ≦ d ≦ 0.65)
A step of obtaining a gallium-doped transition metal compound represented by
Mixing the gallium-doped transition metal compound and lithium hydroxide to obtain a mixture,
Heat treating the mixture,
A method for producing a positive electrode active material for an all-solid-state lithium-ion battery, comprising: 前記ニッケル、コバルト及びマンガンで構成される遷移金属化合物が水酸化物である請求項１に記載の全固体リチウムイオン電池用正極活物質の製造方法。   The method for producing a positive electrode active material for an all-solid-state lithium ion battery according to claim 1, wherein the transition metal compound composed of nickel, cobalt and manganese is a hydroxide. 前記遷移金属化合物に添加するガリウム化合物がクエン酸ガリウムである請求項１又は２に記載の全固体リチウムイオン電池用正極活物質の製造方法。   The method for producing a positive electrode active material for an all-solid-state lithium-ion battery according to claim 1 or 2, wherein the gallium compound added to the transition metal compound is gallium citrate. 請求項１〜３のいずれか一項に記載の全固体リチウムイオン電池用正極活物質の製造方法によって製造された全固体リチウムイオン電池用正極活物質を用いて正極層を形成し、前記正極層、固体電解質層及び負極層を用いて全固体リチウムイオン電池を製造する全固体リチウムイオン電池の製造方法。   A positive electrode layer is formed using the positive electrode active material for all solid lithium ion batteries manufactured by the manufacturing method of the positive electrode active material for all solid lithium ion batteries as described in any one of Claims 1-3, The said positive electrode layer A method for manufacturing an all-solid-state lithium-ion battery, which manufactures an all-solid-state lithium-ion battery using a solid electrolyte layer and a negative electrode layer.
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