JP2009099461A - Manufacturing method of cathode active material, cathode electrode plate for non-aqueous secondary battery, and non-aqueous secondary battery - Google Patents

Manufacturing method of cathode active material, cathode electrode plate for non-aqueous secondary battery, and non-aqueous secondary battery Download PDF

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JP2009099461A
JP2009099461A JP2007271498A JP2007271498A JP2009099461A JP 2009099461 A JP2009099461 A JP 2009099461A JP 2007271498 A JP2007271498 A JP 2007271498A JP 2007271498 A JP2007271498 A JP 2007271498A JP 2009099461 A JP2009099461 A JP 2009099461A
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positive electrode
active material
electrode active
secondary battery
lithium
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JP5139024B2 (en
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Kazuhiro Okawa
和宏 大川
Yutaka Koyama
裕 小山
Tomoyoshi Ueki
智善 上木
Takuichi Arai
卓一 荒井
Koichi Yokoyama
康一 横山
Riyuuichi Kuzuo
竜一 葛尾
Katsuya Kase
克也 加瀬
Shuhei Oda
周平 小田
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Sumitomo Metal Mining Co Ltd
Toyota Motor Corp
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Toyota Motor Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a cathode active material capable of increasing a capacity of a non-aqueous secondary battery, a cathode electrode plate for the non-aqueous secondary battery capable of increasing the capacity of the non-aqueous secondary battery, and a non-aqueous secondary battery with a large capacity. <P>SOLUTION: The manufacturing method of the cathode active material 153 having a lithium-metal compound oxide as a main component is provided with a surface treatment process (step S15) in which an untreated cathode active material 154 which is formed by calcining a material of the cathode active material 153 is made to contact with a treatment aqueous solution which is adjusted to pH 10-13. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、正極活物質の製造方法、並びに、この製造方法によって製造された正極活物質を備えた非水系二次電池用正極板、及び、これを備えた非水系二次電池に関する。   The present invention relates to a method for producing a positive electrode active material, a positive electrode plate for a non-aqueous secondary battery provided with a positive electrode active material produced by this production method, and a non-aqueous secondary battery comprising the same.

リチウムイオン二次電池等の非水系二次電池は、ポータブル機器や携帯機器などの電源として、また、電気自動車やハイブリッド自動車などの電源として注目されている。近年、リチウム二次電池の特性を良好とすべく、様々な正極活物質の製造方法が提案されている（例えば、特許文献１参照）。   Non-aqueous secondary batteries such as lithium ion secondary batteries are attracting attention as power sources for portable devices and portable devices, and as power sources for electric vehicles and hybrid vehicles. In recent years, various positive electrode active material manufacturing methods have been proposed to improve the characteristics of lithium secondary batteries (see, for example, Patent Document 1).

特開２００５−８５４７１号公報JP 2005-85471 A

特許文献１には、リチウムを含む正極活物質（リチウム−金属複合酸化物）とバインダ樹脂と水とを混練してなる組成物（正極ペースト）を、金属からなる正極集電部材（アルミニウム箔など）の表面に塗布し、その後乾燥等させて、二次電池用正極を製造する方法が開示されている。特に、組成物（正極ペースト）を作製する際、水系溶媒にリチウム塩を添加すると良いことが記載されている。リチウム塩を添加することにより、水系溶媒中にリチウム塩から供給されたリチウムイオンを存在させることができる。これにより、正極活物質から水系溶媒中にリチウムが溶出する現象を抑制することができるので、容量密度の高い正極活物質を備えた正極、二次電池を製造できると記載されている。   Patent Document 1 discloses a composition (positive electrode paste) obtained by kneading a positive electrode active material (lithium-metal composite oxide) containing lithium, a binder resin, and water, and a positive electrode current collecting member (aluminum foil or the like) made of metal. ), And then dried, etc., to produce a secondary battery positive electrode. In particular, it is described that when preparing a composition (positive electrode paste), a lithium salt may be added to an aqueous solvent. By adding the lithium salt, lithium ions supplied from the lithium salt can be present in the aqueous solvent. Accordingly, it is described that a phenomenon in which lithium is eluted from the positive electrode active material into the aqueous solvent can be suppressed, so that a positive electrode and a secondary battery including a positive electrode active material having a high capacity density can be manufactured.

ところで、リチウム−金属複合酸化物からなる正極活物質の表面に、リチウム塩（炭酸リチウムなど）の被膜が生成していることがある。例えば、炭酸リチウムの被膜は、正極活物質の原料を焼成する際、空気中の二酸化炭素ガスとリチウムとが反応して形成されると考えられる。特に、近年、リチウムイオン二次電池等の非水系二次電池について、更なる高容量化、高出力化の要求が高まっており、この要求に応えるべく、正極活物質の結晶格子中に占めるリチウムの割合を高める技術が提案されている。具体的には、例えば、リチウムを理論値よりも過剰に添加して、正極活物質の原料を混合し、この混合物を焼成する。これにより、正極活物質の結晶格子中におけるリチウムの欠損を抑制することができるが、その一方、このようにすると、正極活物質の表面に生成するリチウム塩（炭酸リチウムなど）の被膜が増大してしまう。   Incidentally, a film of a lithium salt (such as lithium carbonate) may be formed on the surface of the positive electrode active material made of a lithium-metal composite oxide. For example, it is considered that the lithium carbonate film is formed by the reaction of carbon dioxide gas in the air and lithium when firing the raw material of the positive electrode active material. In particular, in recent years, there has been an increasing demand for higher capacity and higher output for non-aqueous secondary batteries such as lithium ion secondary batteries, and in order to meet these demands, lithium in the crystal lattice of the positive electrode active material has increased. Techniques that increase the proportion of these have been proposed. Specifically, for example, lithium is added in excess of the theoretical value, the raw materials for the positive electrode active material are mixed, and the mixture is fired. This can suppress lithium deficiency in the crystal lattice of the positive electrode active material. On the other hand, this increases the film of lithium salt (lithium carbonate or the like) formed on the surface of the positive electrode active material. End up.

このような正極活物質を担持した正極板を用いた非水系二次電池では、正極活物質の表面を被覆するリチウム塩の被膜により、充放電時における正極活物質からのＬｉイオンの脱離及び挿入が妨げられてしまい、電池容量や出力特性の低下を引き起こす虞があった。例えば、特許文献１に開示されている上述の手法により非水系二次電池を製造しても、正極活物質の表面を被覆するリチウム塩の被膜の影響で、高容量な非水系二次電池を得ることができなかった。   In a non-aqueous secondary battery using a positive electrode plate supporting such a positive electrode active material, the lithium salt coating covering the surface of the positive electrode active material causes the desorption of Li ions from the positive electrode active material during charge / discharge and Insertion was hindered, and there was a risk of causing a decrease in battery capacity and output characteristics. For example, even if a non-aqueous secondary battery is manufactured by the above-described method disclosed in Patent Document 1, a high-capacity non-aqueous secondary battery is produced under the influence of a lithium salt coating that covers the surface of the positive electrode active material. Couldn't get.

本発明は、かかる現状に鑑みてなされたものであって、非水系二次電池の容量を高めることができる正極活物質の製造方法、及び非水系二次電池の容量を高めることができる非水系二次電池用正極板、並びに、高容量な非水系二次電池を提供することを目的とする。   The present invention has been made in view of the current situation, and is a method for producing a positive electrode active material capable of increasing the capacity of a non-aqueous secondary battery, and a non-aqueous system capable of increasing the capacity of a non-aqueous secondary battery. It aims at providing the positive electrode plate for secondary batteries, and a high capacity | capacitance non-aqueous secondary battery.

その解決手段は、リチウム−金属複合酸化物を主成分とする正極活物質の製造方法であって、上記正極活物質の原料を焼成してなる未処理正極活物質を、ｐＨ１０〜１３に調整した処理水溶液に接触させる表面処理工程を備える正極活物質の製造方法である。   The solution is a method for producing a positive electrode active material containing a lithium-metal composite oxide as a main component, and the untreated positive electrode active material obtained by firing the raw material of the positive electrode active material is adjusted to pH 10-13. It is a manufacturing method of a positive electrode active material provided with the surface treatment process made to contact process aqueous solution.

本発明の製造方法では、正極活物質の原料を焼成してなる未処理正極活物質（表面処理工程を行う前の正極活物質をいう、以下同じ）を、ｐＨ１０〜１３に調整した処理水溶液に接触させて表面処理する。これにより、正極活物質（リチウム−金属複合酸化物）中からＬｉイオンが溶出するのを抑制しつつ、正極活物質（リチウム−金属複合酸化物）の表面を被覆しているリチウム塩の少なくとも一部を除去することができる。従って、本発明の製造方法によれば、非水系二次電池の容量を高めることが可能な、容量密度の高い正極活物質を得ることができる。   In the production method of the present invention, an untreated positive electrode active material obtained by firing a raw material of a positive electrode active material (referred to as a positive electrode active material before the surface treatment step, hereinafter the same) is adjusted to a treated aqueous solution adjusted to pH 10-13. Surface treatment by contact. Accordingly, at least one of the lithium salts covering the surface of the positive electrode active material (lithium-metal composite oxide) while suppressing the elution of Li ions from the positive electrode active material (lithium-metal composite oxide). Part can be removed. Therefore, according to the production method of the present invention, it is possible to obtain a positive electrode active material having a high capacity density capable of increasing the capacity of the non-aqueous secondary battery.

なお、ｐＨ１０〜１３に調整した処理水溶液としては、例えば、ｐＨ１０〜１３の水酸化リチウム水溶液を用いることができる。
また、リチウム−金属複合酸化物からなる正極活物質としては、例えば、複合ニッケル酸リチウム（ＬｉＮｉ1-X-YＣｏXＡｌYＯ2 など）や、複合コバルト酸リチウム等を挙げることができる。 In addition, as processing aqueous solution adjusted to pH10-13, lithium hydroxide aqueous solution of pH10-13 can be used, for example.
Examples of the positive electrode active material made of a lithium-metal composite oxide include composite lithium nickelate (such as LiNi 1-XY Co X Al Y O 2 ) and composite lithium cobaltate.

さらに、上記の正極活物質の製造方法であって、前記表面処理工程は、前記未処理正極活物質を前記処理水溶液に浸漬し、上記処理水溶液と共に撹拌する正極活物質の製造方法とするのが好ましい。   Furthermore, in the method for producing a positive electrode active material, the surface treatment step may be a method for producing a positive electrode active material in which the untreated positive electrode active material is immersed in the treatment aqueous solution and stirred together with the treatment aqueous solution. preferable.

未処理正極活物質を浸漬した処理水溶液を撹拌することで、各正極活物質粒子を、むら無く、処理水溶液に接触させることができる。従って、この製造方法によれば、非水系二次電池の容量を高めることが可能な、容量密度の高い正極活物質を、効率良く得ることができる。   By stirring the treatment aqueous solution in which the untreated positive electrode active material is immersed, each positive electrode active material particle can be brought into contact with the treatment aqueous solution without unevenness. Therefore, according to this manufacturing method, a positive electrode active material having a high capacity density that can increase the capacity of the non-aqueous secondary battery can be obtained efficiently.

さらに、上記いずれかの正極活物質の製造方法であって、前記未処理正極活物質は、前記正極活物質の原料のうち、リチウム成分のモル数Ｘと、これ以外の金属成分のモル数Ｙとのモル比Ｘ／Ｙを、１．０２以上１．１０以下の範囲内として焼成した未処理正極活物質である正極活物質の製造方法とすると良い。   Furthermore, in any one of the above-described methods for producing a positive electrode active material, the untreated positive electrode active material includes a number of moles X of lithium components and a number of moles Y of other metal components among the raw materials of the positive electrode active material. And the molar ratio X / Y is preferably in the range of 1.02 or more and 1.10 or less, and is a method for producing a positive electrode active material that is an untreated positive electrode active material.

正極活物質の原料のうち、リチウム成分のモル数Ｘと、これ以外の金属成分のモル数Ｙとのモル比Ｘ／Ｙを、１．０２以上１．１０以下の範囲内として焼成することで、リチウム−金属複合酸化物の結晶格子中におけるリチウムの欠損を抑制することができる。すなわち、エネルギー密度の高い正極活物質（リチウム−金属複合酸化物）を得ることができる。その一方、リチウム成分を理論値よりも過剰に添加して焼成するため、正極活物質（リチウム−金属複合酸化物）の表面に、平均厚みが１０ｎｍ程度のリチウム塩からなる被膜が形成されてしまうので、この被膜の影響で、充放電時における正極活物質からのＬｉイオンの脱離及び挿入が妨げられる虞がある。   By calcining the raw material of the positive electrode active material such that the molar ratio X / Y of the number of moles X of the lithium component and the number of moles Y of the other metal components is in the range of 1.02 to 1.10. , Lithium deficiency in the crystal lattice of the lithium-metal composite oxide can be suppressed. That is, a positive electrode active material (lithium-metal composite oxide) having a high energy density can be obtained. On the other hand, since the lithium component is added in excess of the theoretical value and fired, a film made of a lithium salt having an average thickness of about 10 nm is formed on the surface of the positive electrode active material (lithium-metal composite oxide). Therefore, there is a possibility that the desorption and insertion of Li ions from the positive electrode active material during charging / discharging may be hindered by the influence of this coating film.

しかしながら、この未処理正極活物質（平均厚み１０ｎｍ程度のリチウム塩で被覆されたリチウム−金属複合酸化物）についても、前述のように表面処理を行うことで、容易に、正極活物質の表面を被覆しているリチウム塩の少なくとも一部を除去することができる。従って、本発明の製造方法によれば、非水系二次電池の容量を高めることが可能な、容量密度の高い正極活物質を、適切に得ることができる。   However, this untreated positive electrode active material (lithium-metal composite oxide coated with a lithium salt having an average thickness of about 10 nm) is also surface treated as described above, so that the surface of the positive electrode active material can be easily treated. At least a part of the covering lithium salt can be removed. Therefore, according to the production method of the present invention, a positive electrode active material having a high capacity density and capable of increasing the capacity of the nonaqueous secondary battery can be obtained appropriately.

さらに、上記いずれかの正極活物質の製造方法であって、前記表面処理工程は、前記未処理正極活物質を前記処理水溶液に浸漬し、上記処理水溶液の導電率が９０ｍＳ／ｃｍを上回る前に、表面処理を終了する正極活物質の製造方法とすると良い。   Furthermore, in any one of the methods for producing a positive electrode active material, the surface treatment step includes immersing the untreated positive electrode active material in the treatment aqueous solution, and before the conductivity of the treatment aqueous solution exceeds 90 mS / cm. The positive electrode active material is preferably manufactured by finishing the surface treatment.

前述のように、未処理正極活物質を、ｐＨ１０〜１３に調整した処理水溶液で表面処理することで、正極活物質の表面を被覆しているリチウム塩の少なくとも一部を除去することができる。しかしながら、表面処理し過ぎると、正極活物質（リチウム−金属複合酸化物）中から多量のＬｉイオンが溶出してしまい、却って、正極活物質の容量密度を低下させてしまう虞がある。従って、表面処理工程において、表面処理し過ぎないように、表面処理の程度を客観的に把握することが重要となる。   As described above, at least a part of the lithium salt covering the surface of the positive electrode active material can be removed by surface-treating the untreated positive electrode active material with a treatment aqueous solution adjusted to pH 10 to 13. However, if the surface treatment is excessive, a large amount of Li ions are eluted from the positive electrode active material (lithium-metal composite oxide), and on the contrary, the capacity density of the positive electrode active material may be reduced. Therefore, in the surface treatment process, it is important to objectively grasp the degree of the surface treatment so as not to overtreat the surface.

ところで、正極活物質を表面処理する処理水溶液の導電率は、溶出したＬｉイオンの増加に伴い上昇する。すなわち、正極活物質の表面を被覆しているリチウム塩由来のＬｉイオン、及び、正極活物質（リチウム−金属複合酸化物）を構成しているリチウム由来のＬｉイオンの増加に伴い、処理水溶液の導電率は上昇する。   By the way, the electrical conductivity of the treatment aqueous solution for surface-treating the positive electrode active material increases as the eluted Li ions increase. That is, with the increase of Li ions derived from lithium salt covering the surface of the positive electrode active material and Li ions derived from lithium constituting the positive electrode active material (lithium-metal composite oxide), The conductivity increases.

そこで、本発明の製造方法では、未処理正極活物質を処理水溶液に浸漬し（これを撹拌しても良い）、この処理水溶液の導電率が９０ｍＳ／ｃｍを上回る前に表面処理を終了することにした。これにより、正極活物質の表面を被覆しているリチウム塩の少なくとも一部を除去することができ、しかも、表面処理し過ぎることなく、正極活物質（リチウム−金属複合酸化物）からのＬｉイオンの溶出を、適切に抑制することができる。従って、本発明の製造方法によれば、非水系二次電池の容量を高めることが可能な、容量密度の高い正極活物質を、適切に得ることができる。
なお、未処理正極活物質を浸漬した処理水溶液を撹拌することで、好適に、容量密度の高い正極活物質を得ることができるので好ましい。 Therefore, in the production method of the present invention, the untreated positive electrode active material is immersed in a treated aqueous solution (which may be stirred), and the surface treatment is terminated before the electrical conductivity of the treated aqueous solution exceeds 90 mS / cm. I made it. Thereby, at least a part of the lithium salt covering the surface of the positive electrode active material can be removed, and the Li ion from the positive electrode active material (lithium-metal composite oxide) can be removed without excessive surface treatment. Can be appropriately suppressed. Therefore, according to the production method of the present invention, a positive electrode active material having a high capacity density and capable of increasing the capacity of the nonaqueous secondary battery can be obtained appropriately.
In addition, since the positive electrode active material with a high capacity | capacitance density can be obtained suitably by stirring the process aqueous solution which immersed the untreated positive electrode active material, it is preferable.

さらに、上記いずれかの正極活物質の製造方法であって、前記未処理正極活物質は、前記リチウム−金属複合酸化物の表面が、平均厚み５〜１５ｎｍのリチウム塩で被覆された未処理正極活物質である正極活物質の製造方法とするのが好ましい。
平均厚み５〜１５ｎｍのリチウム塩の被膜を有する未処理正極活物質について、前述のように、処理水溶液による表面処理処理を行うことで、容易に、容量密度の高い正極活物質を得ることができる。 Furthermore, in any one of the above-described methods for producing a positive electrode active material, the untreated positive electrode active material is obtained by coating the surface of the lithium-metal composite oxide with a lithium salt having an average thickness of 5 to 15 nm. A method for producing a positive electrode active material which is an active material is preferable.
As described above, a positive electrode active material having a high capacity density can be easily obtained by subjecting an untreated positive electrode active material having a lithium salt film having an average thickness of 5 to 15 nm to a surface treatment with a treatment aqueous solution as described above. .

他の解決手段は、前記いずれかの正極活物質の製造方法により製造された正極活物質と、上記正極活物質を担持する正極集電部材と、を備える非水系二次電池用正極板である。   Another solution is a positive electrode plate for a non-aqueous secondary battery comprising: a positive electrode active material produced by any one of the above-described methods for producing a positive electrode active material; and a positive electrode current collecting member supporting the positive electrode active material. .

本発明の非水系二次電池用正極板は、正極活物質として、ｐＨ１０〜１３に調整した処理水溶液に接触させて表面処理した正極活物質を有している。このように表面処理した正極活物質は、前述のように、非水系二次電池の容量を高めることが可能な、容量密度の高い正極活物質となっている。従って、非水系二次電池用正極板は、非水系二次電池の容量を高めることが可能な非水系二次電池用正極板となる。   The positive electrode plate for a non-aqueous secondary battery of the present invention has a positive electrode active material that has been surface-treated by contacting with a treatment aqueous solution adjusted to pH 10 to 13 as a positive electrode active material. As described above, the surface-treated positive electrode active material is a positive electrode active material having a high capacity density capable of increasing the capacity of the non-aqueous secondary battery. Therefore, the positive electrode plate for a non-aqueous secondary battery is a positive electrode plate for a non-aqueous secondary battery that can increase the capacity of the non-aqueous secondary battery.

他の解決手段は、上記の非水系二次電池用正極板と、負極板と、セパレータとを含む電極体を備える非水系二次電池である。   Another solution is a non-aqueous secondary battery including an electrode body including the positive electrode plate for a non-aqueous secondary battery, a negative electrode plate, and a separator.

本発明の非水系二次電池では、非水系二次電池用正極板として、ｐＨ１０〜１３に調整した処理水溶液に接触させて表面処理した正極活物質を有する正極板を用いている。この非水系二次電池用正極板は、前述のように、非水系二次電池の容量を高めることが可能な正極板である。従って、本発明の非水系二次電池は、高容量な非水系二次電池となる。   In the non-aqueous secondary battery of the present invention, a positive electrode plate having a positive electrode active material that has been surface-treated by contacting with a treatment aqueous solution adjusted to pH 10 to 13 is used as the positive electrode plate for the non-aqueous secondary battery. As described above, the positive electrode plate for a non-aqueous secondary battery is a positive electrode plate that can increase the capacity of the non-aqueous secondary battery. Therefore, the non-aqueous secondary battery of the present invention is a high-capacity non-aqueous secondary battery.

次に、本発明の実施形態について、図面を参照しつつ説明する。
（実施例１）
まず、本実施例１にかかる非水系二次電池１００について説明する。非水系二次電池１００は、図１に示すように、直方体形状の電池ケース１１０と、正極端子１２０と、負極端子１３０とを備える、角形密閉式のリチウムイオン二次電池である。
電池ケース１１０は、金属からなり、直方体形状の収容空間をなす角形収容部１１１と、金属製の蓋部１１２とを有している。電池ケース１１０（角形収容部１１１）の内部には、電極体１５０、正極集電部材１２２、負極集電部材１３２などが収容されている。正極集電部材１２２及び負極集電部材１３２は、細長板形状の金属部材であり、それぞれ、正極端子１２０及び負極端子１３０に接続されている。 Next, embodiments of the present invention will be described with reference to the drawings.
Example 1
First, the nonaqueous secondary battery 100 according to the first embodiment will be described. As shown in FIG. 1, the nonaqueous secondary battery 100 is a rectangular sealed lithium ion secondary battery including a rectangular parallelepiped battery case 110, a positive electrode terminal 120, and a negative electrode terminal 130.
The battery case 110 is made of metal, and includes a rectangular housing portion 111 that forms a rectangular parallelepiped housing space, and a metal lid portion 112. An electrode body 150, a positive current collecting member 122, a negative current collecting member 132, and the like are accommodated in the battery case 110 (rectangular accommodation portion 111). The positive electrode current collecting member 122 and the negative electrode current collecting member 132 are elongated metal members, and are connected to the positive electrode terminal 120 and the negative electrode terminal 130, respectively.

電極体１５０は、断面長円状をなし、シート状の正極板１５５、負極板１５６、及びセパレータ１５７を捲回してなる扁平型の捲回体である。この電極体１５０は、その軸線方向（図１において左右方向）の一方端部（図１において右端部）に位置し、正極板１５５の一部のみが渦巻状に重なる正極捲回部１５５ｂと、他方端部（図１において左端部）に位置し、負極板１５６の一部のみが渦巻状に重なる負極捲回部１５６ｂとを有している。正極板１５５には、正極捲回部１５５ｂを除く部位に、正極活物質を含む正極合材が塗工されている。同様に、負極板１５６には、負極捲回部１５６ｂを除く部位に、負極活物質を含む負極合材が塗工されている。   The electrode body 150 is an oblong cross-section, and is a flat wound body that is formed by winding a sheet-like positive electrode plate 155, a negative electrode plate 156, and a separator 157. The electrode body 150 is positioned at one end portion (right end portion in FIG. 1) in the axial direction (left and right direction in FIG. 1), and a positive electrode winding portion 155b in which only a part of the positive electrode plate 155 overlaps in a spiral shape, It is located at the other end (left end in FIG. 1) and has a negative electrode winding part 156b in which only a part of the negative electrode plate 156 overlaps spirally. A positive electrode mixture containing a positive electrode active material is coated on the positive electrode plate 155 at a portion other than the positive electrode winding portion 155b. Similarly, the negative electrode plate 156 is coated with a negative electrode mixture containing a negative electrode active material at a portion other than the negative electrode winding portion 156b.

ここで、正極板１５５について、図２を参照して詳細に説明する。正極板１５５は、図２に示すように、アルミニウム箔からなる正極集電部材１５１と、この正極集電部材１５１の表面に塗布された正極合材１５２とを有している。正極合材１５２は、正極活物質１５３と、導電化材１５９（本実施例１では、アセチレンブラック，ケッチェンブラックなど）と、図示しないバインダ樹脂（本実施例１では、ＣＭＣ，ＰＥＯ，ＰＴＦＥ）とを有している。なお、正極活物質１５３は、複合ニッケル酸リチウム（ＬｉＮｉ1-X-YＣｏXＡｌYＯ2 など）を主成分としている。 Here, the positive electrode plate 155 will be described in detail with reference to FIG. As shown in FIG. 2, the positive electrode plate 155 includes a positive electrode current collecting member 151 made of an aluminum foil and a positive electrode mixture 152 applied to the surface of the positive electrode current collecting member 151. The positive electrode mixture 152 includes a positive electrode active material 153, a conductive material 159 (in this embodiment 1, acetylene black, ketjen black, etc.), and a binder resin (not shown) (in this embodiment 1, CMC, PEO, PTFE). And have. Note that the positive electrode active material 153 contains composite lithium nickelate (such as LiNi 1-XY Co X Al Y O 2 ) as a main component.

次に、本実施例１の非水系二次電池１００の製造方法について説明する。
（正極活物質の作製）
図４に示すように、ステップＳ１において、正極活物質１５３を製造した。
具体的には、図５に示すように、ステップＳ１１において、公知の反応晶析法（例えば、特開２００６−１２７９５５参照）により、一次粒子の凝集した球状の二次粒子からなる、コバルト及びアルミニウム含有水酸化ニッケルを製造した。次いで、ステップＳ１２に進み、このコバルト及びアルミニウム含有水酸化ニッケルを、１０００℃程度で焙焼して酸化物とした後、この酸化物と水酸化リチウム一水和物とを混合した。 Next, a method for manufacturing the non-aqueous secondary battery 100 of the first embodiment will be described.
(Preparation of positive electrode active material)
As shown in FIG. 4, in step S1, a positive electrode active material 153 was manufactured.
Specifically, as shown in FIG. 5, in step S11, cobalt and aluminum composed of spherical secondary particles in which primary particles are aggregated by a known reaction crystallization method (see, for example, JP-A-2006-127955). Containing nickel hydroxide was produced. Subsequently, it progressed to step S12, this cobalt and aluminum containing nickel hydroxide was roasted at about 1000 degreeC, and it was set as the oxide, Then, this oxide and lithium hydroxide monohydrate were mixed.

なお、本実施例１では、この混合物におけるリチウム成分のモル数Ｘと、これ以外の金属成分（本実施例１では、ニッケル、コバルト、及びアルミニウム）のモル数Ｙとのモル比Ｘ／Ｙが、１．０２以上１．１０以下の範囲内となるようにしている。このように、リチウム成分を理論値よりも過剰に添加することで、焼成後のリチウム−金属複合酸化物の結晶格子中におけるリチウムの欠損を、好適に抑制することができる。すなわち、エネルギー密度の高い正極活物質（リチウム−金属複合酸化物）を得ることができる。   In Example 1, the molar ratio X / Y between the number of moles X of the lithium component in this mixture and the number of moles Y of the other metal components (in Example 1, nickel, cobalt, and aluminum) is 1.02 or more and 1.10 or less. Thus, the lithium defect | deletion in the crystal lattice of the lithium-metal composite oxide after baking can be suppressed suitably by adding a lithium component excessively than a theoretical value. That is, a positive electrode active material (lithium-metal composite oxide) having a high energy density can be obtained.

次いで、ステップＳ１３に進み、この混合物を電気炉内に配置し、５００℃程度の温度で、３時間程度仮焼きした。これに引き続き、ステップＳ１４（焼成工程）に進み、７３０℃程度の温度で、２０時間程度焼成した。その後、解砕処理をすることで、多数の球状微粒子（未処理正極活物質１５４、図３参照）を得ることができた。   Subsequently, it progressed to step S13, this mixture was arrange | positioned in an electric furnace, and it calcined for about 3 hours at the temperature of about 500 degreeC. Following this, the process proceeds to step S14 (firing step), and baked at a temperature of about 730 ° C. for about 20 hours. Thereafter, by crushing, a large number of spherical fine particles (untreated positive electrode active material 154, see FIG. 3) could be obtained.

得られた未処理正極活物質１５４の断面（図３参照）を、透過電子顕微鏡（ＴＥＭ）を用いて観察したところ、この未処理正極活物質１５４は、複合ニッケル酸リチウムからなる多数の一次粒子１５３ｂが焼結した二次粒子１５３ｃと、この二次粒子１５３ｃの表面を被覆するリチウム塩１５８（図３にハッチングで示す）とにより構成されていることが確認できた。さらに、二次粒子１５３ｃ（複合ニッケル酸リチウム）の表面を被覆するリチウム塩１５８の厚みを調査したところ、その平均厚みは１０ｎｍであった。   When the cross section (see FIG. 3) of the obtained untreated positive electrode active material 154 was observed using a transmission electron microscope (TEM), this untreated positive electrode active material 154 was composed of a large number of primary particles composed of composite lithium nickelate. It was confirmed that 153b was composed of sintered secondary particles 153c and a lithium salt 158 (shown by hatching in FIG. 3) covering the surfaces of the secondary particles 153c. Furthermore, when the thickness of the lithium salt 158 covering the surfaces of the secondary particles 153c (composite lithium nickelate) was examined, the average thickness was 10 nm.

また、リチウム塩１５８は、炭酸リチウムと硫酸リチウムを含んでいることが確認できた。なお、炭酸リチウムは、ステップＳ１３，Ｓ１４において、空気中の二酸化炭素ガスと、正極活物質中のリチウムとが反応することで生成されたと考えられる。また、硫酸リチウムは、ステップＳ１３，Ｓ１４において、正極活物質中に存在する硫酸根とリチウムとが反応して生成されたと考えられる。特に、本実施例１では、リチウム成分を理論値よりも過剰に添加して（具体的には、１．０２≦Ｘ／Ｙ≦１．１０）焼成しているため、リチウム−金属複合酸化物の表面に、平均厚み１０ｎｍ程度の厚いリチウム塩の被膜が形成されてしまった。   Further, it was confirmed that the lithium salt 158 contains lithium carbonate and lithium sulfate. In addition, it is thought that lithium carbonate was produced | generated by reacting the carbon dioxide gas in air and lithium in a positive electrode active material in step S13, S14. In addition, it is considered that lithium sulfate was generated by reacting the sulfate radical present in the positive electrode active material with lithium in steps S13 and S14. In particular, in Example 1, since the lithium component was added in excess of the theoretical value (specifically, 1.02 ≦ X / Y ≦ 1.10), the lithium-metal composite oxide was fired. A thick lithium salt film having an average thickness of about 10 nm was formed on the surface.

次に、ステップＳ１５（表面処理工程）に進み、未処理正極活物質１５４（球状微粒子）を、ｐＨ１０〜１３に調整した処理水溶液に接触させて表面処理した。具体的には、処理水溶液として、ｐＨ１１に調整した液温３０℃の水酸化リチウム水溶液を用意し、この水酸化リチウム水溶液５００ｇ中に、５００ｇの未処理正極活物質１５４を投入、浸漬した。そして、プロペラ攪拌機（ＡＳ ＯＮＥ製）を用いて、２００ｒｐｍの回転数で２０分間撹拌した。その後、球状微粒子を乾燥させることで、正極活物質１５３を得た。   Next, it progressed to step S15 (surface treatment process), and surface-treated the untreated positive electrode active material 154 (spherical fine particle) by making it contact with the process aqueous solution adjusted to pH10-13. Specifically, a lithium hydroxide aqueous solution having a liquid temperature of 30 ° C. adjusted to pH 11 was prepared as a treatment aqueous solution, and 500 g of the untreated positive electrode active material 154 was charged and immersed in 500 g of this lithium hydroxide aqueous solution. And it stirred for 20 minutes at the rotation speed of 200 rpm using the propeller stirrer (made by AS ONE). Then, the positive electrode active material 153 was obtained by drying spherical fine particles.

なお、本実施例１では、所定時間毎に処理水溶液の導電率を測定した。具体的には、撹拌開始から所定時間経過したときに、処理水溶液２０ｇを採取し、これを吸引濾過する。なお、本実施例１では、アスピレータＡＳ−０１（ＡＳ ＯＮＥ製）を用いて、採取した処理水溶液を吸引し、これを＃５Ｃのろ紙でろ過した。そして、得られたろ液の導電率を、導電率計（ＹＯＫＯＧＡＷＡ ＳＣ８２）を用いて測定した。   In Example 1, the conductivity of the treatment aqueous solution was measured every predetermined time. Specifically, when a predetermined time has elapsed from the start of stirring, 20 g of the aqueous treatment solution is collected and filtered with suction. In Example 1, the collected treatment aqueous solution was sucked using an aspirator AS-01 (manufactured by AS ONE), and filtered with # 5C filter paper. And the electrical conductivity of the obtained filtrate was measured using the electrical conductivity meter (YOKOGAWA SC82).

測定した処理水溶液の導電率は、処理時間の経過に伴って上昇していた。これは、処理時間の経過に伴って、水酸化リチウム水溶液中に、未処理正極活物質１５４からＬｉイオンの溶出が進行し、Ｌｉイオンが増加していったことによるものと考えられる。このＬｉイオンは、主に、二次粒子１５３ｃ（複合ニッケル酸リチウム）の表面を被覆しているリチウム塩１５８から溶出したＬｉイオンであると考えられる。従って、ステップＳ１５（表面処理工程）において、二次粒子１５３ｃ（複合ニッケル酸リチウム）の表面を被覆するリチウム塩１５８の少なくとも一部を除去することができたといえる。
なお、本実施例１では、２０分間の表面処理を終えたときの処理水溶液の導電率が６２．２ｍＳ／ｃｍであった。 The measured conductivity of the treatment aqueous solution increased with the lapse of treatment time. This is considered to be because the elution of Li ions progressed from the untreated positive electrode active material 154 and the Li ions increased in the lithium hydroxide aqueous solution as the treatment time passed. This Li ion is considered to be mainly Li ions eluted from the lithium salt 158 covering the surface of the secondary particles 153c (composite lithium nickelate). Therefore, it can be said that at least a part of the lithium salt 158 covering the surfaces of the secondary particles 153c (composite lithium nickelate) could be removed in step S15 (surface treatment process).
In Example 1, the electrical conductivity of the aqueous treatment solution after finishing the surface treatment for 20 minutes was 62.2 mS / cm.

（正極板の作製）
次に、図４に示すように、ステップＳ２に進み、正極板１５５を作製した。
具体的には、図６に示すように、ステップＳ２１（正極ペースト作製工程）において、上述のようにして得た正極活物質１５３と、導電化材１５９（アセチレンブラック，ケッチェンブラック）と、水系バインダ樹脂（ＣＭＣ，ＰＥＯ，ＰＴＦＥ）と、水とを混合し、正極ペーストを作製した。なお、正極活物質１５３と、導電化材１５９と、水系バインダ樹脂とは、８７：１０：３の割合（重量比）で添加している。 (Preparation of positive electrode plate)
Next, as shown in FIG. 4, it progressed to step S2 and the positive electrode plate 155 was produced.
Specifically, as shown in FIG. 6, in step S21 (positive electrode paste manufacturing process), the positive electrode active material 153 obtained as described above, the conductive material 159 (acetylene black, ketjen black), and an aqueous system A binder resin (CMC, PEO, PTFE) and water were mixed to prepare a positive electrode paste. Note that the positive electrode active material 153, the conductive material 159, and the aqueous binder resin are added in a ratio (weight ratio) of 87: 10: 3.

次いで、ステップＳ２２（塗布工程）に進み、この正極ペーストを、正極集電部材１５１（厚み１５μｍのアルミニウム箔）の表面に塗布した。その後、ステップＳ２３に進み、ペーストを塗布した正極集電部材１５１にプレス加工を施し、押圧成形して正極シートを得た。次いで、ステップＳ２４に進み、この正極シートを、１２０℃で８時間真空乾燥し、その後冷却することで、正極板１５５を得た。   Subsequently, it progressed to step S22 (application | coating process), and this positive electrode paste was apply | coated to the surface of the positive electrode current collection member 151 (15-micrometer-thick aluminum foil). Then, it progressed to step S23, the positive electrode current collection member 151 which apply | coated the paste was pressed, and it press-molded, and obtained the positive electrode sheet. Subsequently, it progressed to step S24, this positive electrode sheet was vacuum-dried at 120 degreeC for 8 hours, and the positive electrode plate 155 was obtained by cooling after that.

（電池の作製）
また、図４に示すように、ステップＳ３において、負極活物質（カーボン粉末）とバインダ樹脂とを混合したペーストを、負極基材（銅箔）の表面に塗布し、プレス加工を施して、負極板１５６を作製した。
次に、ステップＳ４に進み、正極板１５５、負極板１５６、及びセパレータ１５７を積層し、これを捲回して断面長円状の電極体１５０を形成した。 (Production of battery)
Further, as shown in FIG. 4, in step S3, a paste in which a negative electrode active material (carbon powder) and a binder resin are mixed is applied to the surface of the negative electrode base material (copper foil), pressed, and subjected to a negative electrode. A plate 156 was produced.
Next, it progressed to step S4, the positive electrode plate 155, the negative electrode plate 156, and the separator 157 were laminated | stacked, and this was wound, and the cross-sectional ellipse-shaped electrode body 150 was formed.

次いで、ステップＳ５に進み、非水系二次電池１００の組み付けを行った。具体的には、電極体１５０を外部端子（正極端子１２０と負極端子１３０）と接続させると共に、角形収容部１１１内に収容した。その後、角形収容部１１１と蓋体１１２とを溶接して、電池ケース１１０を封止した（図１参照）。次いで、蓋体１１２に設けられている注液口（図示しない）を通じて電解液を注液した後、注液口を封止することで、本実施例１の非水系二次電池１００が完成する。   Subsequently, it progressed to step S5 and the non-aqueous secondary battery 100 was assembled | attached. Specifically, the electrode body 150 was connected to external terminals (the positive electrode terminal 120 and the negative electrode terminal 130), and was accommodated in the square accommodating portion 111. Thereafter, the square housing part 111 and the lid body 112 were welded to seal the battery case 110 (see FIG. 1). Next, after injecting an electrolyte through an injection port (not shown) provided in the lid 112, the injection port is sealed, thereby completing the nonaqueous secondary battery 100 of the first embodiment. .

（実施例２〜４）
実施例２〜４では、ステップＳ１５（表面処理工程）において、実施例１とはｐＨ値が異なる処理水溶液（水酸化リチウム水溶液）を用いて、未処理正極活物質１５４（球状微粒子）の表面処理を行った。具体的には、実施例２，３，４では、この順に、ｐＨ＝１０，１２．５，１３の処理水溶液を用いて、未処理正極活物質１５４（球状微粒子）を表面処理し、正極活物質２５３，３５３，４５３を得た。この正極活物質２５３〜４５３を用いることの他は、実施例１と同様にして、非水系二次電池２００〜４００を製造した。 (Examples 2 to 4)
In Examples 2 to 4, the surface treatment of the untreated positive electrode active material 154 (spherical fine particles) using a treatment aqueous solution (lithium hydroxide aqueous solution) having a pH value different from that in Example 1 in Step S15 (surface treatment step). Went. Specifically, in Examples 2, 3, and 4, the untreated positive electrode active material 154 (spherical fine particles) was surface-treated in this order using the treatment aqueous solutions with pH = 10, 12.5, and 13 to obtain the positive electrode active material. Material 253,353,453 was obtained. Nonaqueous secondary batteries 200 to 400 were manufactured in the same manner as in Example 1 except that the positive electrode active materials 253 to 453 were used.

また、比較例１〜４として、この順に、ｐＨ＝５，７，９，１４に調整した処理水溶液を用いて未処理正極活物質１５４（球状微粒子）を表面処理し、正極活物質を得た。さらに、比較例５として、未処理正極活物質１５４（球状微粒子）の表面処理を行うことなく、未処理正極活物質１５４を正極活物質として得た。そして、各正極活物質を用いて、実施例１と同様にして、比較例１〜５の非水系二次電池を製造した。
なお、比較例１では、ｐＨ５の処理水溶液として、硫酸水溶液を用いている。 Further, as Comparative Examples 1 to 4, the untreated positive electrode active material 154 (spherical fine particles) was surface-treated in this order using the treatment aqueous solution adjusted to pH = 5, 7, 9, 14 to obtain a positive electrode active material. . Further, as Comparative Example 5, an untreated positive electrode active material 154 was obtained as a positive electrode active material without performing surface treatment of the untreated positive electrode active material 154 (spherical fine particles). And the nonaqueous secondary battery of Comparative Examples 1-5 was manufactured like Example 1 using each positive electrode active material.
In Comparative Example 1, a sulfuric acid aqueous solution is used as the pH 5 treatment aqueous solution.

（電池の評価）
次に、実施例１〜４の非水系二次電池１００〜４００、及び、比較例１〜５の非水系二次電池について、それぞれ、ＣＣＣＶ容量を測定した。
具体的には、各非水系二次電池について、電池電圧が３Ｖになるまで、１Ｃの電流値で放電を行い、引き続き、定電流（１Ｃ）−定電圧（３Ｖ）で放電を行い、計２時間の放電を行った。次いで、１０分間放置した後、電池電圧が４．１Ｖになるまで、１Ｃの電流値で充電し、引き続き、定電流（１Ｃ）−定電圧（４．１Ｖ）で充電し、計２時間の充電を行った。 (Battery evaluation)
Next, the CCCV capacities of the nonaqueous secondary batteries 100 to 400 of Examples 1 to 4 and the nonaqueous secondary batteries of Comparative Examples 1 to 5 were measured.
Specifically, each non-aqueous secondary battery is discharged at a current value of 1 C until the battery voltage reaches 3 V, and subsequently discharged at a constant current (1 C) -constant voltage (3 V), for a total of 2 Time discharge was performed. Next, after standing for 10 minutes, the battery is charged at a current value of 1 C until the battery voltage reaches 4.1 V, and subsequently charged at a constant current (1 C) -constant voltage (4.1 V) for a total of 2 hours. Went.

次いで、３０分間放置した後、電池電圧が３Ｖになるまで、１／３Ｃの電流値で放電を行った。このときの放電量をＤ１として取得した。引き続いて、定電流（１／３Ｃ）−定電圧（３Ｖ）で、２時間放電を行った。このときの放電量をＤ２として取得した。そして、Ｄ１とＤ２との和（Ｄ１＋Ｄ２）を、各非水系二次電池のＣＣＣＶ容量として得た。
その後、実施例１の非水系二次電池１００（ｐＨ１１の処理水溶液で表面処理した正極活物質１５３を用いた電池）のＣＣＣＶ容量を基準（１００％）として、各非水系二次電池のＣＣＣＶ容量比（％）を算出した。 Next, after leaving for 30 minutes, the battery was discharged at a current value of 1/3 C until the battery voltage reached 3V. The amount of discharge at this time was acquired as D1. Subsequently, discharge was performed for 2 hours at a constant current (1/3 C) -constant voltage (3 V). The amount of discharge at this time was acquired as D2. And the sum (D1 + D2) of D1 and D2 was obtained as the CCCV capacity of each non-aqueous secondary battery.
Thereafter, the CCCV capacity of each non-aqueous secondary battery was determined based on the CCCV capacity of the non-aqueous secondary battery 100 of Example 1 (battery using the positive electrode active material 153 surface-treated with a pH 11 treated aqueous solution). The ratio (%) was calculated.

その結果、実施例１〜４の非水系二次電池１００〜４００では、ＣＣＣＶ容量比がそれぞれ、約９９％、１００％、約９９％、約９８％となった。また、比較例１〜５では、順に、約８０％、９０％、約９６％、約９２％、約９５％となった。これらのＣＣＣＶ容量比に基づいて作成したグラフを、図７に示す。
図７に示すように、処理水溶液のｐＨ値を１０〜１３とすることで、大きな電池容量を得られることがわかる。 As a result, in the nonaqueous secondary batteries 100 to 400 of Examples 1 to 4, the CCCV capacity ratios were about 99%, 100%, about 99%, and about 98%, respectively. Moreover, in Comparative Examples 1-5, it became about 80%, 90%, about 96%, about 92%, and about 95% in order. A graph created based on these CCCV capacity ratios is shown in FIG.
As shown in FIG. 7, it can be seen that a large battery capacity can be obtained by setting the pH value of the treatment aqueous solution to 10-13.

一方、処理水溶液のｐＨ値を１０未満とすると、電池容量が小さくなることがわかる。特に、処理水溶液のｐＨ値を７以下とした比較例１，２では、表面処理を行っていない比較例５よりも、電池容量が小さくなってしまった。これは、処理水溶液のｐＨ値が小さくなるにしたがって、Ｌｉイオンが溶出し易くなるので、リチウム塩の被膜のみならず、複合ニッケル酸リチウムから多量のＬｉイオンが溶出したためと考えられる。この結果、正極活物質の容量低下、及び、正極活物質の結晶構造の崩壊を引き起こし、電池容量を低下してしまったと考えられる。   On the other hand, when the pH value of the treatment aqueous solution is less than 10, it can be seen that the battery capacity becomes small. In particular, in Comparative Examples 1 and 2 in which the pH value of the treatment aqueous solution was 7 or less, the battery capacity was smaller than in Comparative Example 5 in which the surface treatment was not performed. This is presumably because a large amount of Li ions were eluted not only from the lithium salt coating but also from the composite lithium nickelate because Li ions were more likely to elute as the pH value of the treatment aqueous solution was decreased. As a result, it is considered that the capacity of the positive electrode active material is reduced and the crystal structure of the positive electrode active material is collapsed, so that the battery capacity is reduced.

また、処理水溶液のｐＨ値を１３より大きくしても、電池容量が小さくなることがわかる。特に、処理水溶液のｐＨ値を１４とした比較例４では、表面処理を行っていない比較例５よりも、電池容量が小さくなってしまった。これは、正極集電部材の腐食の影響によるものと考えられる。具体的には、ｐＨ値が１４の処理水溶液で表面処理を行った正極活物質と水とを混合して作製した正極ペーストが強アルカリ性となり、これを塗工した正極集電部材（アルミニウム箔）の腐食が進行してしまったためと考えられる。   Further, it can be seen that even when the pH value of the treatment aqueous solution is larger than 13, the battery capacity is reduced. In particular, in Comparative Example 4 in which the pH value of the treatment aqueous solution was 14, the battery capacity was smaller than in Comparative Example 5 in which the surface treatment was not performed. This is considered to be due to the influence of corrosion of the positive electrode current collector. Specifically, a positive electrode paste prepared by mixing a positive electrode active material surface-treated with a treatment aqueous solution having a pH value of 14 and water becomes strongly alkaline, and a positive electrode current collecting member (aluminum foil) coated with the positive paste This is thought to be due to the progress of corrosion.

以上より、未処理正極活物質１５４を、ｐＨ１０〜１３に調整した処理水溶液に接触させて表面処理することで、非水系二次電池の容量を高めることが可能な、容量密度の高い正極活物質を得ることができるといえる。これは、ｐＨ１０〜１３に調整した処理水溶液に接触させて表面処理することで、リチウム−金属複合酸化物中からＬｉイオンが溶出するのを抑制しつつ、リチウム−金属複合酸化物（二次粒子１５３ｃ）の表面を被覆しているリチウム塩１５８を除去することができるためと考えられる。   As described above, a high-capacity positive electrode active material capable of increasing the capacity of a non-aqueous secondary battery by bringing the untreated positive electrode active material 154 into contact with a treatment aqueous solution adjusted to pH 10 to 13 and subjecting it to a surface treatment. It can be said that can be obtained. This is because the surface treatment is performed by contacting with a treatment aqueous solution adjusted to pH 10 to 13, while suppressing the elution of Li ions from the lithium-metal composite oxide, the lithium-metal composite oxide (secondary particles) This is probably because the lithium salt 158 covering the surface of 153c) can be removed.

（実施例６）
前述のように、未処理正極活物質１５４を、ｐＨ１０〜１３に調整した処理水溶液に接触させて表面処理することで、非水系二次電池の容量を高めることが可能な、容量密度の高い正極活物質を得ることができることがわかった。しかしながら、表面処理し過ぎると、正極活物質（リチウム−金属複合酸化物）中から多量のＬｉイオンが溶出してしまい、却って、正極活物質の容量密度を低下させてしまう虞がある。従って、表面処理工程において、表面処理し過ぎないように、表面処理の程度を客観的に把握することが重要となる。 (Example 6)
As described above, a high capacity positive electrode capable of increasing the capacity of a non-aqueous secondary battery by bringing the untreated positive electrode active material 154 into contact with a treatment aqueous solution adjusted to pH 10 to 13 and subjecting it to a surface treatment. It was found that an active material can be obtained. However, if the surface treatment is excessive, a large amount of Li ions are eluted from the positive electrode active material (lithium-metal composite oxide), and on the contrary, the capacity density of the positive electrode active material may be reduced. Therefore, in the surface treatment process, it is important to objectively grasp the degree of the surface treatment so as not to overtreat the surface.

そこで、本実施例６では、表面処理工程（ステップ１５）において、実施例１と同様のｐＨ１１の処理水溶液を用いて、表面処理時間（撹拌時間）を１５〜１２０分の間で異ならせて、表面処理の適切な範囲を調査した。具体的には、表面処理時間（撹拌時間）を、１５分、２０分（実施例１に相当する）、３０分、６０分、１２０分と異ならせて、５種類の正極活物質を得た。なお、本実施例６でも、実施離１と同様に、処理水溶液（水酸化リチウム水溶液）に、これと等重量の未処理正極活物質１５４を加えて、表面処理を行っている。
また、実施例１と同様にして、各表面処理時間（撹拌時間）が経過したときの各処理水溶液の導電率を測定したところ、上記の順に、４８．７ｍＳ／ｃｍ、６２．２ｍＳ／ｃｍ、７５．０ｍＳ／ｃｍ、９１．５ｍＳ／ｃｍ、１０５．０ｍＳ／ｃｍであった。 Therefore, in this Example 6, in the surface treatment step (Step 15), using the treatment aqueous solution having the same pH of 11 as in Example 1, the surface treatment time (stirring time) is varied between 15 to 120 minutes, The appropriate range of surface treatment was investigated. Specifically, the surface treatment time (stirring time) was changed to 15 minutes, 20 minutes (corresponding to Example 1), 30 minutes, 60 minutes, and 120 minutes to obtain five types of positive electrode active materials. . In Example 6, as in Example 1, the surface treatment was performed by adding the untreated positive electrode active material 154 in an equal weight to the treated aqueous solution (lithium hydroxide aqueous solution).
Moreover, when the electrical conductivity of each treatment aqueous solution when each surface treatment time (stirring time) passed was measured in the same manner as in Example 1, 48.7 mS / cm, 62.2 mS / cm, 75.0 mS / cm, 91.5 mS / cm, and 105.0 mS / cm.

さらに、上記５種類の正極活物質をそれぞれ用いて、５種類の非水系二次電池（順に、サンプル１〜５とする）を製造した。その後、サンプル１〜５について、実施例１と同様にして、ＣＣＣＶ容量を測定し、表面処理時間（撹拌時間）を２０分としたサンプル２（実施例１に相当）のＣＣＣＶ容量を基準（１００％）として、各非水系二次電池のＣＣＣＶ容量比（％）を算出した。この結果を表１に示す。なお、比較のため、表面処理を施していない比較例５のデータも併せて記載している。   Furthermore, five types of non-aqueous secondary batteries (referred to as samples 1 to 5 in this order) were manufactured using the five types of positive electrode active materials, respectively. Thereafter, the CCCV capacity of Samples 1 to 5 was measured in the same manner as in Example 1, and the CCCV capacity of Sample 2 (corresponding to Example 1) with a surface treatment time (stirring time) of 20 minutes was used as a reference (100 %), The CCCV capacity ratio (%) of each non-aqueous secondary battery was calculated. The results are shown in Table 1. For comparison, data of Comparative Example 5 that has not been subjected to surface treatment is also shown.

Figure 2009099461
Figure 2009099461

表１からわかるように、処理水溶液の導電率は、処理時間の経過に伴って上昇する。これは、処理時間の経過に伴って、水酸化リチウム水溶液中に、未処理正極活物質１５４からＬｉイオンの溶出が進行し、Ｌｉイオンが増加していったことによるものと考えられる。詳細には、表面処理を開始すると、主にリチウム塩の被膜から溶出したＬｉイオンにより処理水溶液の導電率が上昇してゆき、やがて、リチウム塩の被膜からのみならず、リチウム−金属複合酸化物中からもＬｉイオンが溶出することから、処理水溶液の導電率が大きくなってゆくと考えられる。従って、処理水溶液の導電率によって、表面処理の適切な範囲を決めることができるといえる。   As can be seen from Table 1, the conductivity of the treatment aqueous solution increases with the lapse of treatment time. This is considered to be because the elution of Li ions progressed from the untreated positive electrode active material 154 and the Li ions increased in the lithium hydroxide aqueous solution as the treatment time passed. Specifically, when the surface treatment is started, the electrical conductivity of the treatment aqueous solution is increased mainly by Li ions eluted from the lithium salt coating, and eventually the lithium-metal composite oxide not only from the lithium salt coating. Since Li ions are eluted from the inside, it is considered that the conductivity of the treatment aqueous solution increases. Therefore, it can be said that an appropriate range of the surface treatment can be determined by the conductivity of the treatment aqueous solution.

具体的に検討すると、処理水溶液の導電率が９０ｍＳ／ｃｍを上回る前に表面処理を終了したサンプル１〜３では、ＣＣＣＶ容量比がそれぞれ、約９９％、１００％、約９８％となり、表面処理を施していない比較例５（約９５％）に比べて、電池容量を大きくすることができた。これは、リチウム−金属複合酸化物中からＬｉイオンが溶出するのを抑制しつつ、リチウム−金属複合酸化物（二次粒子１５３ｃ）の表面を被覆しているリチウム塩１５８を除去することができるためと考えられる。   Specifically, in Samples 1 to 3 where the surface treatment was completed before the conductivity of the treatment aqueous solution exceeded 90 mS / cm, the CCCV capacity ratios were about 99%, 100%, and about 98%, respectively. The battery capacity could be increased as compared with Comparative Example 5 (about 95%) that was not applied. This can remove the lithium salt 158 covering the surface of the lithium-metal composite oxide (secondary particles 153c) while suppressing the elution of Li ions from the lithium-metal composite oxide. This is probably because of this.

ところが、処理水溶液の導電率が９０ｍＳ／ｃｍを上回った後も表面処理を行ったサンプル４，５では、ＣＣＣＶ容量比がそれぞれ、約９４％、約９０％となり、表面処理を施していない比較例５（約９５％）に比べて、電池容量を小さくなってしまった。これは、表面処理し過ぎて、リチウム塩の被膜からのみならず、リチウム−金属複合酸化物中からも多量のＬｉイオンが溶出したためであると考えられる。   However, in the samples 4 and 5 in which the surface treatment was performed even after the conductivity of the treated aqueous solution exceeded 90 mS / cm, the CCCV capacity ratios were about 94% and about 90%, respectively. Compared to 5 (about 95%), the battery capacity has become smaller. This is presumably because the surface treatment was excessive and a large amount of Li ions were eluted not only from the lithium salt coating but also from the lithium-metal composite oxide.

以上の結果より、処理水溶液の導電率が９０ｍＳ／ｃｍを上回る前に表面処理を終了することで、非水系二次電池の容量を高めることが可能な、容量密度の高い正極活物質を、適切に得ることができるといえる。特に、サンプル１〜３の結果より、処理水溶液の導電率が４５〜７５ｍＳ／ｃｍの範囲の値に達したときに表面処理を終了することで、特に容量密度の高い正極活物質を得ることができるといえる。   From the above results, a positive electrode active material with a high capacity density that can increase the capacity of the non-aqueous secondary battery by finishing the surface treatment before the electrical conductivity of the treatment aqueous solution exceeds 90 mS / cm is suitable. It can be said that it can be obtained. In particular, from the results of Samples 1 to 3, it is possible to obtain a positive electrode active material having a particularly high capacity density by terminating the surface treatment when the conductivity of the treatment aqueous solution reaches a value in the range of 45 to 75 mS / cm. I can say that.

以上において、本発明を実施例１〜６に即して説明したが、本発明は上記実施例等に限定されるものではなく、その要旨を逸脱しない範囲で、適宜変更して適用できることはいうまでもない。   In the above, the present invention has been described with reference to the first to sixth embodiments. However, the present invention is not limited to the above-described embodiments and the like, and can be applied with appropriate modifications without departing from the gist thereof. Not too long.

実施例にかかる非水系二次電池１００の断面図である。It is sectional drawing of the non-aqueous secondary battery 100 concerning an Example. 非水系二次電池１００の正極板１５５の拡大断面図である。3 is an enlarged cross-sectional view of a positive electrode plate 155 of a non-aqueous secondary battery 100. FIG. 未処理正極活物質１５４の拡大断面図である。3 is an enlarged cross-sectional view of an untreated positive electrode active material 154. FIG. 非水系二次電池１００の製造の流れを示すフローチャートである。3 is a flowchart showing a flow of manufacturing the non-aqueous secondary battery 100. 未処理正極活物質１５４の製造の流れを示すフローチャートである。5 is a flowchart showing a flow of manufacturing an untreated positive electrode active material 154. 正極板１５５の製造の流れを示すフローチャートである。5 is a flowchart showing a flow of manufacturing a positive electrode plate 155. 処理水溶液のｐＨとＣＣＣＶ容量比との関係を示すグラフである。It is a graph which shows the relationship between pH of a process aqueous solution, and a CCCV capacity | capacitance ratio.

符号の説明Explanation of symbols

１００，２００，３００，４００ 非水系二次電池
１５０ 電極体
１５１ 正極集電部材
１５３ 正極活物質
１５３ｂ 一次粒子
１５３ｃ 二次粒子
１５４ 未処理正極活物質
１５５ 正極板（非水系二次電池用正極板）
１５６ 負極板
１５７ セパレータ
１５８ リチウム塩 100, 200, 300, 400 Nonaqueous secondary battery 150 Electrode body 151 Positive electrode current collecting member 153 Positive electrode active material 153b Primary particle 153c Secondary particle 154 Untreated positive electrode active material 155 Positive electrode plate (positive electrode plate for nonaqueous secondary battery)
156 Negative electrode plate 157 Separator 158 Lithium salt

Claims (5)

リチウム−金属複合酸化物を主成分とする正極活物質の製造方法であって、
上記正極活物質の原料を焼成してなる未処理正極活物質を、ｐＨ１０〜１３に調整した処理水溶液に接触させる表面処理工程を備える
正極活物質の製造方法。 A method for producing a positive electrode active material mainly comprising a lithium-metal composite oxide,
The manufacturing method of a positive electrode active material provided with the surface treatment process which makes the process aqueous solution adjusted to pH 10-13 the untreated positive electrode active material formed by baking the raw material of the said positive electrode active material. 請求項１に記載の正極活物質の製造方法であって、
前記未処理正極活物質は、
前記正極活物質の原料のうち、リチウム成分のモル数Ｘと、これ以外の金属成分のモル数Ｙとのモル比Ｘ／Ｙを、１．０２以上１．１０以下の範囲内として焼成した未処理正極活物質である
正極活物質の製造方法。 It is a manufacturing method of the positive electrode active material of Claim 1, Comprising:
The untreated positive electrode active material is
Of the raw materials for the positive electrode active material, the raw material of the positive electrode active material was not fired by setting the molar ratio X / Y of the mole number X of the lithium component and the mole number Y of the other metal component to be in the range of 1.02 to 1.10 The manufacturing method of the positive electrode active material which is a process positive electrode active material. 請求項１または請求項２に記載の正極活物質の製造方法であって、
前記表面処理工程は、
前記未処理正極活物質を前記処理水溶液に浸漬し、上記処理水溶液の導電率が９０ｍＳ／ｃｍを上回る前に、表面処理を終了する
正極活物質の製造方法。 It is a manufacturing method of the positive electrode active material of Claim 1 or Claim 2, Comprising:
The surface treatment step includes
A method for producing a positive electrode active material, wherein the untreated positive electrode active material is immersed in the treatment aqueous solution, and the surface treatment is terminated before the conductivity of the treatment aqueous solution exceeds 90 mS / cm. 請求項１〜請求項３のいずれか一項に記載の正極活物質の製造方法により製造された正極活物質と、
上記正極活物質を担持する正極集電部材と、を備える
非水系二次電池用正極板。 The positive electrode active material manufactured by the manufacturing method of the positive electrode active material as described in any one of Claims 1-3,
A positive electrode plate for a non-aqueous secondary battery, comprising: a positive electrode current collecting member supporting the positive electrode active material. 請求項４に記載の非水系二次電池用正極板と、負極板と、セパレータとを含む電極体を備える
非水系二次電池。 A nonaqueous secondary battery comprising an electrode body comprising the positive electrode plate for a nonaqueous secondary battery according to claim 4, a negative electrode plate, and a separator.
JP2007271498A 2007-10-18 2007-10-18 Method for producing positive electrode active material, positive electrode plate for non-aqueous secondary battery, and non-aqueous secondary battery Active JP5139024B2 (en)

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