JP2013125648A - Positive electrode active material for lithium ion battery, and lithium ion battery - Google Patents

Positive electrode active material for lithium ion battery, and lithium ion battery Download PDF

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JP2013125648A
JP2013125648A JP2011273776A JP2011273776A JP2013125648A JP 2013125648 A JP2013125648 A JP 2013125648A JP 2011273776 A JP2011273776 A JP 2011273776A JP 2011273776 A JP2011273776 A JP 2011273776A JP 2013125648 A JP2013125648 A JP 2013125648A
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lithium ion
positive electrode
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JP5804419B2 (en
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Shiho Ishihara
四穂 石原
Hiroki Yamashita
弘樹 山下
Tsutomu Suzuki
務 鈴木
Kiyoshi Kanemura
聖志 金村
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Taiheiyo Cement Corp
Tokyo Metropolitan Public University Corp
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Tokyo Metropolitan Public University 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

PROBLEM TO BE SOLVED: To provide a positive electrode active material for a lithium ion battery, containing an olivine-type silicate compound composed of primary particles and secondary particles having a specific size and shape and exhibiting an excellent battery physical property, and a lithium ion battery obtained from the same.SOLUTION: A positive electrode active material for a lithium ion battery contains an olivine-type silicate compound represented by LiMSiO(where M represents one or two kinds or more selected from Fe, Ni, Co, and Mn.) The olivine-type silicate compound has secondary particles having an average grain size of 1-100 μm, and the secondary particles being an aggregation of spherical primary particles having an average grain size of 20-100 nm.

Description

本発明は、リチウムイオン電池用正極活物質及びそれから得られるリチウムイオン電池に関する。   The present invention relates to a positive electrode active material for a lithium ion battery and a lithium ion battery obtained therefrom.

リチウムイオン電池は、非水電解質電池の１種であり、携帯電話、デジタルカメラ、ノートＰＣ、ハイブリッド自動車、電気自動車等広い分野に利用されている。リチウムイオン電池は、正極材料としてリチウム金属酸化物を用い、負極材料としてグラファイトなどの炭素材を用いるものが主流となっている。   Lithium ion batteries are a type of non-aqueous electrolyte battery and are used in a wide range of fields such as mobile phones, digital cameras, notebook PCs, hybrid cars, and electric cars. Lithium ion batteries mainly use lithium metal oxide as a positive electrode material and a carbon material such as graphite as a negative electrode material.

この正極材料としては、コバルト酸リチウム（ＬｉＣｏＯ2）、マンガン酸リチウム（ＬｉＭｎＯ2）、リン酸鉄リチウム（ＬｉＦｅＰＯ4）、ケイ酸鉄リチウム（Ｌｉ2ＦｅＳｉＯ4）等が知られている。このうち、ＬｉＦｅＰＯ4やＬｉ2ＦｅＳｉＯ4等は、オリビン構造を有し、高容量のリチウムイオン電池用正極材料として有用である。なかでも、ＬｉＦｅＰＯ4等のリン酸リチウム金属系正極材料は、得られる電池物性のさらなる向上を図るべく、形成される粒子の粒径、粒度分布、形状等を制御したものが知られている（特許文献１、２）。 As this positive electrode material, lithium cobaltate (LiCoO 2 ), lithium manganate (LiMnO 2 ), lithium iron phosphate (LiFePO 4 ), lithium iron silicate (Li 2 FeSiO 4 ) and the like are known. Among these, LiFePO 4 and Li 2 FeSiO 4 have an olivine structure and are useful as a positive electrode material for a high capacity lithium ion battery. Among these, lithium metal phosphate-based positive electrode materials such as LiFePO 4 are known in which the particle size, particle size distribution, shape, and the like of the formed particles are controlled in order to further improve the physical properties of the obtained battery ( Patent Documents 1 and 2).

一方、Ｌｉ2ＦｅＳｉＯ4等のケイ酸リチウム金属系正極材料の製造法としては、Ｌｉ源、鉄（金属）源及びケイ酸源の混合物を粉砕し、５００〜９００℃で焼成するという固相法が一般的である（特許文献３、４）。しかし、固相法では、不活性ガス雰囲気での焼成と粉砕を行う必要があり、複雑な操作が必要であるとともに、粒径や結晶度を制御することが困難である。
これに対し、非特許文献１には、Ｌｉ2Ｍｎ1-yＦｅyＳｉＯ4（ｙ＝０〜１）を水熱合成で得られる旨の記載がある。 On the other hand, as a method for producing a lithium silicate metal positive electrode material such as Li 2 FeSiO 4 , a solid phase method in which a mixture of a Li source, an iron (metal) source and a silicate source is pulverized and fired at 500 to 900 ° C. Is common (Patent Documents 3 and 4). However, in the solid phase method, it is necessary to perform firing and pulverization in an inert gas atmosphere, which requires complicated operations and it is difficult to control the particle size and crystallinity.
On the other hand, Non-Patent Document 1 describes that Li 2 Mn 1-y Fe y SiO 4 (y = 0 to 1) can be obtained by hydrothermal synthesis.

特許第４１９０９１２号公報Japanese Patent No. 4190912 特開２００６−３２２４１号公報JP 2006-32241 A 特開２００１−２６６８８２号公報JP 2001-266882 A 特開２００２−１９８０５０号公報JP 2002-198050 A

ＧＳ Ｙｕａｓａ Ｔｅｃｈｎｉｃａｌ Ｒｅｐｏｒｔ ２００９年６月、第６巻、第１号、ｐ２１−２６GS Yuasa Technical Report June 2009, Vol. 6, No. 1, p21-26

こうしたなか、発明者らによって、ケイ酸リチウム金属系正極材料を構成する一次粒子径を微細化すれば、電池物性がさらに向上することが判明したものの、従来のように、リチウム源、鉄源及びシリケート源の３者を水に混合し、その混合液をそのまま水熱反応に付しても、得られるＬｉ2ＦｅＳｉＯ4の粒径を充分に制御することができないことも判明した。そのため、Ｌｉ2ＦｅＳｉＯ4等のケイ酸リチウム金属系正極材料については、電池物性を充分に向上し得る、一次粒子や二次粒子の制御された粒径を有するものは未だ知られていないのが実情である。 Under these circumstances, the inventors have found that if the primary particle size constituting the lithium metal silicate-based positive electrode material is made finer, the battery physical properties are further improved. It was also found that even when the three silicate sources were mixed with water and the mixture was subjected to a hydrothermal reaction as it was, the particle diameter of the resulting Li 2 FeSiO 4 could not be controlled sufficiently. Therefore, for lithium metal silicate positive electrode materials such as Li 2 FeSiO 4, those having a controlled particle size of primary particles and secondary particles that can sufficiently improve battery physical properties are not yet known. It is a fact.

したがって、本発明の課題は、特定の粒径及び形状を有する一次粒子及び二次粒子からなるオリビン型シリケート化合物を含有し、優れた電池物性を発揮するリチウムイオン電池用正極活物質及びそれから得られるリチウムイオン電池を提供することにある。   Accordingly, an object of the present invention is to provide a positive electrode active material for a lithium ion battery that contains an olivine-type silicate compound composed of primary particles and secondary particles having a specific particle size and shape, and exhibits excellent battery properties, and obtained therefrom. The object is to provide a lithium ion battery.

そこで本発明者らは、微細化された球状一次粒子を凝集させて粒径が制御された二次粒子を有するオリビン型シリケート化合物を用いることにより、優れた電池物性を発揮するリチウムイオン電池用正極活物質が得られることを見出し、本発明を完成するに至った。   Accordingly, the present inventors have developed a positive electrode for a lithium ion battery that exhibits excellent battery physical properties by using an olivine-type silicate compound having secondary particles whose particle diameter is controlled by agglomerating fine spherical primary particles. The present inventors have found that an active material can be obtained and have completed the present invention.

すなわち、本発明は、Ｌｉ2ＭＳｉＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎから選ばれる１種又は２種以上を示す）で表されるオリビン型シリケート化合物を含有し、
オリビン型シリケート化合物が、平均粒径２０〜１００ｎｍの球状一次粒子が凝集してなる平均粒径１〜１００μｍの二次粒子を有することを特徴とする、リチウムイオン電池用正極活物質を提供するものである。
また、本発明は、上記リチウムイオン電池用正極活物質を含む正極を有するリチウムイオン電池を提供するものである。 That is, the present invention contains an olivine-type silicate compound represented by Li 2 MSiO 4 (wherein M represents one or more selected from Fe, Ni, Co, or Mn),
Provided is a positive electrode active material for a lithium ion battery, characterized in that the olivine-type silicate compound has secondary particles having an average particle diameter of 1 to 100 μm formed by agglomerating spherical primary particles having an average particle diameter of 20 to 100 nm. It is.
Moreover, this invention provides the lithium ion battery which has a positive electrode containing the said positive electrode active material for lithium ion batteries.

本発明のリチウムイオン電池用正極活物質によれば、高容量で充放電特性に優れたリチウムイオン電池が得られる。   According to the positive electrode active material for a lithium ion battery of the present invention, a lithium ion battery having a high capacity and excellent charge / discharge characteristics can be obtained.

実施例１で得られたオリビン型シリケート化合物を構成する球状一次粒子のＳＥＭ像を示す。The SEM image of the spherical primary particle which comprises the olivine type | mold silicate compound obtained in Example 1 is shown. 実施例１で得られたオリビン型シリケート化合物を構成する二次粒子のＳＥＭ像を示す。The SEM image of the secondary particle which comprises the olivine type | mold silicate compound obtained in Example 1 is shown. 図２で示す二次粒子の一部のＴＥＭ像を示す。The TEM image of a part of secondary particle shown in FIG. 2 is shown. 実施例１で得られたリチウムイオン電池用正極活物質を用いた電池の充放電曲線を示す。The charging / discharging curve of the battery using the positive electrode active material for lithium ion batteries obtained in Example 1 is shown.

以下、本発明について詳細に説明する。
本発明に用いられるオリビン型シリケート化合物は、Ｌｉ2ＭＳｉＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎから選ばれる１種又は２種以上を示す）で表される。当該オリビン型シリケート化合物の具体例としては、Ｌｉ2ＦｅＳｉＯ4、Ｌｉ2ＮｉＳｉＯ4、Ｌｉ2ＣｏＳｉＯ4、Ｌｉ2ＭｎＳｉＯ4、Ｌｉ2（Ｆｅ）m（Ｍｎ）1-mＳｉＯ4（０＜ｍ＜１である）等が挙げられる。このうち、原料コストの点からＬｉ2ＦｅＳｉＯ4、Ｌｉ2ＭｎＳｉＯ4が好ましく、Ｌｉ2ＦｅＳｉＯ4がより好ましい。 Hereinafter, the present invention will be described in detail.
The olivine-type silicate compound used in the present invention is represented by Li 2 MSiO 4 (wherein M represents one or more selected from Fe, Ni, Co, or Mn). Specific examples of the olivine silicate compound include Li 2 FeSiO 4 , Li 2 NiSiO 4 , Li 2 CoSiO 4 , Li 2 MnSiO 4 , Li 2 (Fe) m (Mn) 1-m SiO 4 (0 <m < 1). Among these, Li 2 FeSiO 4 and Li 2 MnSiO 4 are preferable from the viewpoint of raw material cost, and Li 2 FeSiO 4 is more preferable.

該オリビン型シリケート化合物は、球状一次粒子が凝集してなる二次粒子を有する。該球状一次粒子は、単結晶と見なせる微細な結晶である複数の結晶子によって構成された、球状を呈した粒子である。ここで球状とは、三次元方向へほぼ同等に成長した粒子の形状を意味し、特に真球に限るものではなく、球状に近似したものをも含む。したがって、板状や扁平形状は含まれない。球状一次粒子の平均粒径は、２０〜１００ｎｍであり、好ましくは３０〜７０ｎｍ、より好ましくは３０〜５０ｎｍである。
なお、一次粒子の平均粒径とは、ＳＥＭ観察により求められる値を意味する。具体的には、１１００×８００ｎｍ2視野において、一次粒子をランダムに２０個抽出して求めた粒径の値を平均したものを意味する。 The olivine-type silicate compound has secondary particles formed by agglomerating spherical primary particles. The spherical primary particles are spherical particles composed of a plurality of crystallites which are fine crystals that can be regarded as single crystals. Here, the spherical shape means the shape of particles grown almost equally in the three-dimensional direction, and is not particularly limited to a true sphere, but includes a shape that approximates a sphere. Therefore, plate shape and flat shape are not included. The average particle diameter of the spherical primary particles is 20 to 100 nm, preferably 30 to 70 nm, and more preferably 30 to 50 nm.
In addition, the average particle diameter of a primary particle means the value calculated | required by SEM observation. Specifically, in the 1100 × 800 nm 2 field of view, it means the average of the values of the particle sizes obtained by randomly extracting 20 primary particles.

このように、球状一次粒子は非常に微細な粒子であるため、オリビン型シリケート化合物結晶内におけるリチウムイオンの吸蔵・放出が容易となり、正極材料として電池容量を高めるのに多いに寄与する。また、正極活物質を得るにあたり、一次粒子を凝集させた二次粒子をカーボン担持して焼成した際、カーボンが一次粒子及び二次粒子の表面に均一なカーボン層を形成して粒子間を適度に接合することで、粒子間の間隙を低減することも可能であるため、導電性を充分に高めることができる。   As described above, since the spherical primary particles are very fine particles, it is easy to occlude / release lithium ions in the olivine-type silicate compound crystal, which contributes to increasing the battery capacity as a positive electrode material. In addition, when obtaining the positive electrode active material, when the secondary particles obtained by aggregating the primary particles are supported on carbon and fired, the carbon forms a uniform carbon layer on the surface of the primary particles and the secondary particles, so that the space between the particles is moderate. By bonding the particles to each other, the gap between particles can be reduced, so that the conductivity can be sufficiently increased.

一次粒子及び二次粒子の表面に形成されるカーボン層の厚みは、好ましくは０．１〜３ｎｍであり、より好ましくは１〜２．５ｎｍである。   The thickness of the carbon layer formed on the surfaces of the primary particles and the secondary particles is preferably 0.1 to 3 nm, more preferably 1 to 2.5 nm.

球状一次粒子は、単結晶と見なされる微細結晶である複数の結晶子からなり、該結晶子の粒径は、好ましくは２０〜５０ｎｍであり、より好ましくは２０〜３０ｎｍである。なお、結晶子の粒径は、Ｘ線回折により測定した回折角の半値幅から、デバイ−シェラーの式を用いて求めることができる。   The spherical primary particles are composed of a plurality of crystallites which are fine crystals regarded as single crystals, and the crystallites preferably have a particle size of 20 to 50 nm, more preferably 20 to 30 nm. The crystallite particle size can be determined from the half-value width of the diffraction angle measured by X-ray diffraction using the Debye-Scherrer equation.

複数の微細な球状一次粒子が凝集してなる二次粒子の平均粒径は、１〜１００μｍであり、好ましくは５〜５０μｍであり、より好ましくは５〜２０μｍである。オリビン型シリケート化合物が該二次粒子を有することにより、優れた塗布性を発揮するため、より平滑で均一な電極層を形成することが可能である。
なお、二次粒子の平均粒径とは、一次粒子と同様にＳＥＭ観察により求められる値を意味する。 The average particle diameter of secondary particles formed by agglomerating a plurality of fine spherical primary particles is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 5 to 20 μm. Since the olivine-type silicate compound has the secondary particles, it exhibits excellent coating properties, so that a smoother and more uniform electrode layer can be formed.
In addition, the average particle diameter of secondary particles means the value calculated | required by SEM observation similarly to a primary particle.

本発明のリチウムイオン電池用正極活物質の製造方法は、以下のとおりである。
まずＬｉ2ＭＳｉＯ4で表されるオリビン型シリケート化合物を水熱反応に付して、一次粒子を形成する。水熱反応に付すにあたっては、遷移金属（Ｍ）源を用い、リチウム化合物、ケイ酸化合物及び酸化防止剤を含有する塩基性水分散液を作製するのがよい。 The manufacturing method of the positive electrode active material for lithium ion batteries of this invention is as follows.
First, an olivine type silicate compound represented by Li 2 MSiO 4 is subjected to a hydrothermal reaction to form primary particles. In the hydrothermal reaction, it is preferable to prepare a basic aqueous dispersion containing a lithium compound, a silicate compound and an antioxidant using a transition metal (M) source.

遷移金属（Ｍ）源としては、例えば、ＭＳＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎを示す）で表される遷移金属硫酸塩又は（Ｒ）2Ｍ（式中、Ｒは有機酸残基を示し、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎを示す）で表される有機酸遷移金属塩、或いは（Ｒ）2Ｍ（式中、Ｒは有機酸残基を示し、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎを示す）で表される有機酸遷移金属塩が挙げられる。 As the transition metal (M) source, for example, transition metal sulfate represented by MSO 4 (wherein M represents Fe, Ni, Co or Mn) or (R) 2 M (wherein R is organic) Represents an acid residue, M represents an organic acid transition metal salt represented by Fe, Ni, Co or Mn, or (R) 2 M (wherein R represents an organic acid residue, and M represents Fe , Ni, Co or Mn)).

遷移金属硫酸塩ＭＳＯ4の具体例としては、ＦｅＳＯ4、ＮｉＳＯ4、ＣｏＳＯ4又はＭｎＳＯ4が挙げられ、これらは１種でも２種以上を混合して用いてもよい。これらのうち、ＦｅＳＯ4、ＭｎＳＯ4がより好ましく、ＦｅＳＯ4がさらに好ましい。遷移金属硫酸塩を用いる場合、副反応を抑制する点から、遷移金属硫酸塩とは別に、リチウム化合物、ケイ酸化合物及び酸化防止剤を含有する塩基性水分散液を予め調製しておくのが好ましい。この場合、該水分散液と遷移金属硫酸塩とを混合し、水熱反応に付す。遷移金属硫酸塩の添加量は、反応混合液中０．１５〜１.５０ｍｏｌ／ｌとなる量が好ましく、さらに０．５０〜０．７５ｍｏｌ／ｌとなる量が好ましい。なお、この場合における反応混合液中のＳｉ及びＬｉの含有量は、Ｍに対して２モル以上が好ましい。 Specific examples of the transition metal sulfate MSO 4 include FeSO 4 , NiSO 4 , CoSO 4, and MnSO 4 , and these may be used alone or in combination of two or more. Of these, FeSO 4 and MnSO 4 are more preferable, and FeSO 4 is more preferable. When using a transition metal sulfate, a basic aqueous dispersion containing a lithium compound, a silicate compound and an antioxidant is prepared in advance separately from the transition metal sulfate from the viewpoint of suppressing side reactions. preferable. In this case, the aqueous dispersion and the transition metal sulfate are mixed and subjected to a hydrothermal reaction. The amount of transition metal sulfate added is preferably 0.15 to 1.50 mol / l in the reaction mixture, and more preferably 0.50 to 0.75 mol / l. In this case, the content of Si and Li in the reaction mixture is preferably 2 mol or more with respect to M.

有機酸遷移金属塩（Ｒ）2ＭのＲで示される有機酸としては、炭素数１〜２０の有機酸が好ましく、炭素数２〜１２の有機酸がより好ましい。より具体的な有機酸としては、シュウ酸、フマル酸等のジカルボン酸、乳酸等のヒドロキシカルボン酸、酢酸等の脂肪酸が挙げられる。有機酸遷移金属塩を用いる場合、リチウム化合物、ケイ酸化合物及び酸化防止剤を含有し、さらに有機酸遷移金属塩を含有する塩基性水分散液を調製するのが好ましい。通常、有機酸塩は固相法に用いられる原料であるが、水熱反応に用いることにより副反応を抑制することができる。なお、この場合における反応混合液中のＳｉ及びＬｉは、遷移金属に対してモル比で２倍以上用いることが好ましく、Ｓｉ：Ｌｉ：Ｍが１：１：２．５〜１：１：３程度がより好ましい。 The organic acid represented by an organic acid transition metal salt (R) of 2 M R, preferably an organic acid having 1 to 20 carbon atoms, more preferably an organic acid having 2 to 12 carbon atoms. More specific organic acids include dicarboxylic acids such as oxalic acid and fumaric acid, hydroxycarboxylic acids such as lactic acid, and fatty acids such as acetic acid. When using an organic acid transition metal salt, it is preferable to prepare a basic aqueous dispersion containing a lithium compound, a silicic acid compound and an antioxidant, and further containing an organic acid transition metal salt. Usually, an organic acid salt is a raw material used in a solid phase method, but side reactions can be suppressed by using it in a hydrothermal reaction. In this case, Si and Li in the reaction mixture are preferably used in a molar ratio of 2 or more with respect to the transition metal, and Si: Li: M is from 1: 1: 2.5 to 1: 1: 3. The degree is more preferable.

リチウム化合物としては、水酸化リチウム（例えばＬｉＯＨ・Ｈ2Ｏ）、炭酸リチウム（Ｌｉ2ＣＯ3）、硫酸リチウム、酢酸リチウムが挙げられるが、水酸化リチウム、炭酸リチウムが特に好ましい。水分散液中のリチウム化合物の濃度は、０．３０〜３．００ｍｏｌ／ｌが好ましく、さらに１．００〜１．５０ｍｏｌ／ｌが好ましい。 Examples of the lithium compound include lithium hydroxide (for example, LiOH.H 2 O), lithium carbonate (Li 2 CO 3 ), lithium sulfate, and lithium acetate, and lithium hydroxide and lithium carbonate are particularly preferable. The concentration of the lithium compound in the aqueous dispersion is preferably 0.30 to 3.00 mol / l, more preferably 1.00 to 1.50 mol / l.

ケイ酸化合物としては、反応性のあるシリカ化合物であれば特に限定されず、非晶質シリカ、Ｎａ4ＳｉＯ4（例えばＮａ4ＳｉＯ4・Ｈ2Ｏ）が好ましい。このうちＮａ4ＳｉＯ4を用いた場合、水分散液が塩基性になるので、より好ましい。水分散液中のケイ酸化合物の濃度は、０．１５〜１.５０ｍｏｌ／ｌが好ましく、さらに０．５０〜０．７５ｍｏｌ／ｌが好ましい。 The silicic acid compound is not particularly limited as long as it is a reactive silica compound, and amorphous silica and Na 4 SiO 4 (for example, Na 4 SiO 4 .H 2 O) are preferable. Of these, the use of Na 4 SiO 4 is more preferable because the aqueous dispersion becomes basic. The concentration of the silicate compound in the aqueous dispersion is preferably 0.15 to 1.50 mol / l, more preferably 0.50 to 0.75 mol / l.

酸化防止剤としては、ハイドロサルファイトナトリウム（Ｎａ2Ｓ2Ｏ4）、アンモニア水、亜硫酸ナトリウム等が挙げられる。水分散液中の酸化防止剤の含有量は、多量に添加するとオリビン型シリケート化合物の生成を抑制してしまうため、遷移金属（Ｍ）に対して等モル量以下が好ましく、遷移金属に対してモル比で０．５以下がさらに好ましい。 Examples of the antioxidant include sodium hydrosulfite (Na 2 S 2 O 4 ), aqueous ammonia, sodium sulfite and the like. The content of the antioxidant in the aqueous dispersion is preferably equal to or less than the transition metal (M) because the formation of the olivine-type silicate compound is suppressed when added in a large amount. The molar ratio is more preferably 0.5 or less.

遷移金属源として遷移金属硫酸塩ＭＳＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎを示す）を用いる場合、副反応を抑制する点から、遷移金属硫酸塩とは別に、リチウム化合物、ケイ酸化合物及び酸化防止剤を含有する塩基性水分散液を予め調製しておくのが好ましい。この場合、該水分散液と遷移金属硫酸塩とを混合し、水熱反応に付す。該水分散液の調製にあたって、リチウム化合物、ケイ酸化合物及び酸化防止剤の添加順序は特に限定されず、これらの３成分を水に添加してもよい。 When transition metal sulfate MSO 4 (wherein M represents Fe, Ni, Co, or Mn) is used as the transition metal source, a lithium compound, silica, and silica are separated from the transition metal sulfate from the viewpoint of suppressing side reactions. It is preferable to prepare in advance a basic aqueous dispersion containing an acid compound and an antioxidant. In this case, the aqueous dispersion and the transition metal sulfate are mixed and subjected to a hydrothermal reaction. In preparing the aqueous dispersion, the order of addition of the lithium compound, the silicate compound and the antioxidant is not particularly limited, and these three components may be added to water.

該水分散液は、副反応を防止し、ケイ酸化合物を溶解する点から、塩基性とするのがよい。具体的には、該水分散液のｐＨは、１２．０〜１３．５であるのが好ましい。該水分散液のｐＨの調整は、塩基、例えば、水酸化ナトリウムを添加することにより行ってもよいが、ケイ酸化合物としてＮａ4ＳｉＯ4を用いるのが好ましい。 The aqueous dispersion is preferably basic in terms of preventing side reactions and dissolving the silicate compound. Specifically, the pH of the aqueous dispersion is preferably 12.0 to 13.5. The pH of the aqueous dispersion may be adjusted by adding a base such as sodium hydroxide, but it is preferable to use Na 4 SiO 4 as the silicate compound.

水熱反応は、１００℃以上であればよく、１３０〜１８０℃が好ましく、さらに１４０〜１６０℃が好ましい。水熱反応は耐圧容器中で行うのが好ましく、１３０〜１８０℃で反応を行う場合この時の圧力は０．３〜０．９ＭＰａとなり、１４０〜１６０℃で反応を行う場合の圧力は０．３〜０．４ＭＰａとなる。水熱反応時間は１〜２４時間が好ましく、さらに３〜１２時間が好ましい。   The hydrothermal reaction should just be 100 degreeC or more, 130-180 degreeC is preferable and 140-160 degreeC is more preferable. The hydrothermal reaction is preferably performed in a pressure vessel. When the reaction is performed at 130 to 180 ° C, the pressure at this time is 0.3 to 0.9 MPa, and the pressure when the reaction is performed at 140 to 160 ° C is 0. 3 to 0.4 MPa. The hydrothermal reaction time is preferably 1 to 24 hours, more preferably 3 to 12 hours.

当該水熱反応により、Ｌｉ2ＭＳｉＯ4（Ｍは前記と同じ）が高収率で得られ、その結晶度も高い。水熱反応後、生成したＬｉＭＳｉＯ4をろ過により採取し、洗浄することにより、一次粒子を得るのが好ましい。洗浄は、ケーキ洗浄機能を有した濾過装置を用いて水で行うのが好ましく、次いで乾燥により一次粒子を得る。乾燥手段としては、凍結乾燥又は真空乾燥を用いることができる。 By the hydrothermal reaction, Li 2 MSiO 4 (M is the same as described above) is obtained in a high yield, and its crystallinity is also high. After the hydrothermal reaction, it is preferable to obtain primary particles by collecting and washing the produced LiMSiO 4 by filtration. The washing is preferably carried out with water using a filtration device having a cake washing function, and then primary particles are obtained by drying. As the drying means, freeze drying or vacuum drying can be used.

次に、得られた一次粒子を含有するスラリーを作製し、これを造粒することにより二次粒子を得るのが好ましい。粒径が制御された二次粒子を得るために、かかるスラリー中における一次粒子の含有量や、スラリーの粘度及びｐＨを適宜調整するのがよい。   Next, it is preferable that secondary particles are obtained by preparing a slurry containing the obtained primary particles and granulating the slurry. In order to obtain secondary particles having a controlled particle size, the content of primary particles in the slurry, and the viscosity and pH of the slurry may be appropriately adjusted.

さらに、該スラリーには、適宜、有機バインダー、無機バインダー、導電性炭素材料を含有させてもよい。
有機バインダーとしては、グルコース、フルクトース、ポリエチレングリコール、ポリビニルアルコール、カルボキシメチルセルロース、サッカロース、デンプン、デキストリン、クエン酸等が挙げられる。なかでも、使用量を調整することによって炭素源としても機能し得る点から、グルコース、ポリビニルアルコール、カルボキシメチルセルロースが好ましい。無機バインダーとしては、鱗片状シリカ（二酸化ケイ素）、シリカ−チタニア、ケイ素ガラス、コロイダルシリカ等が挙げられる。 Furthermore, you may make this slurry contain an organic binder, an inorganic binder, and a conductive carbon material suitably.
Examples of the organic binder include glucose, fructose, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose, saccharose, starch, dextrin, and citric acid. Of these, glucose, polyvinyl alcohol, and carboxymethylcellulose are preferred because they can function as a carbon source by adjusting the amount used. Examples of the inorganic binder include scaly silica (silicon dioxide), silica-titania, silicon glass, colloidal silica, and the like.

バインダーとして無機バインダーを用いる場合、導電性炭素材料を併用するのが好ましい。導電性炭素材料としては、カーボンブラックが挙げられ、なかでもアセチレンブラック、ケッチェンブラックが好ましい。導電性炭素材料の使用量は、良好な充放電容量及び経済性の点から、上記一次粒子１００質量部に対し、０．０１〜２０質量部が好ましく、０．１〜１０質量部が好ましい。   When an inorganic binder is used as the binder, it is preferable to use a conductive carbon material in combination. Examples of the conductive carbon material include carbon black, and among them, acetylene black and ketjen black are preferable. The amount of the conductive carbon material used is preferably 0.01 to 20 parts by mass and preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the primary particles from the viewpoint of good charge / discharge capacity and economy.

該スラリーには、溶媒として、水又は有機溶媒を用いてもよい。   In the slurry, water or an organic solvent may be used as a solvent.

造粒は、噴霧乾燥によるものであるのが好ましく、スプレードライ法による噴霧乾燥が最適である。得られた二次粒子は、次いで焼成することにより二次電池用正極活物質として用いることができる。焼成条件は、不活性ガス雰囲気下又は還元条件下に４００℃以上、好ましくは４００〜８００℃で１０分〜３時間、好ましくは０．５〜１．５時間行うのが好ましい。かかる処理により、Ｌｉ2ＭＳｉＯ4表面にカーボンが担持された正極活物質とすることができる。 The granulation is preferably performed by spray drying, and spray drying by a spray drying method is optimal. The obtained secondary particles can then be used as a positive electrode active material for a secondary battery by firing. The firing conditions are 400 ° C. or higher, preferably 400 to 800 ° C. for 10 minutes to 3 hours, preferably 0.5 to 1.5 hours under an inert gas atmosphere or reducing conditions. By such treatment, a positive electrode active material in which carbon is supported on the surface of Li 2 MSiO 4 can be obtained.

得られたリチウムイオン電池用正極活物質は、充放電容量の点で優れており、非常に有用な二次電池を得ることができる。本発明の製造方法により得られるリチウムイオン電池用正極活物質を適用できる二次電池としては、リチウムイオン二次電池であればよく、正極と負極と電解液とセパレータを必須構成とするものであれば特に限定されない。   The obtained positive electrode active material for lithium ion batteries is excellent in terms of charge / discharge capacity, and a very useful secondary battery can be obtained. The secondary battery to which the positive electrode active material for a lithium ion battery obtained by the production method of the present invention can be applied may be a lithium ion secondary battery, and has a positive electrode, a negative electrode, an electrolytic solution, and a separator as essential components. If it does not specifically limit.

ここで、負極については、リチウムイオンを充電時には吸蔵し、かつ放電時には放出することができれば、その材料構成で特に限定されるものではなく、公知の材料構成のものを用いることができる。たとえば、リチウム金属、グラファイト又は非晶質炭素等の炭素材料等である。そしてリチウムを電気化学的に吸蔵・放出し得るインターカレート材料で形成された電極、特に炭素材料を用いることが好ましい。   Here, as long as lithium ions can be occluded at the time of charging and released at the time of discharging, the material structure is not particularly limited, and a known material structure can be used. For example, a carbon material such as lithium metal, graphite, or amorphous carbon. It is preferable to use an electrode formed of an intercalating material capable of electrochemically inserting and extracting lithium, particularly a carbon material.

電解液は、有機溶媒に支持塩を溶解させたものである。有機溶媒は、通常リチウムイオン二次電池の電解液の用いられる有機溶媒であれば特に限定されるものではなく、例えば、カーボネート類、ハロゲン化炭化水素、エーテル類、ケトン類、ニトリル類、ラクトン類、オキソラン化合物等を用いることができる。   The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is usually used for an electrolyte solution of a lithium ion secondary battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones, nitriles, lactones An oxolane compound or the like can be used.

支持塩は、その種類が特に限定されるものではないが、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4及びＬｉＡｓＦ6から選ばれる無機塩、該無機塩の誘導体、ＬｉＳＯ3ＣＦ3、ＬｉＣ（ＳＯ3ＣＦ3）2及びＬｉＮ（ＳＯ3ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2及びＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）から選ばれる有機塩、並びに該有機塩の誘導体の少なくとも１種であることが好ましい。 The type of the supporting salt is not particularly limited, but an inorganic salt selected from LiPF 6 , LiBF 4 , LiClO 4 and LiAsF 6 , a derivative of the inorganic salt, LiSO 3 CF 3 , LiC (SO 3 CF 3 ) 2 and LiN (SO 3 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 and LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), and organic salt derivatives It is preferable that it is at least 1 type of these.

セパレータは、正極及び負極を電気的に絶縁し、電解液を保持する役割を果たすものである。たとえば、多孔性合成樹脂膜、特にポリオレフィン系高分子（ポリエチレン、ポリプロピレン）の多孔膜を用いればよい。   The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.

以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。
［実施例１］
ＬｉＯＨ・Ｈ2Ｏ ４．２０ｇ（０．１ｍｏｌ）、Ｎａ4ＳｉＯ4・ｎＨ2Ｏ ６．９９ｇ（０．０２５ｍｏｌ）、Ｎａ2Ｓ2Ｏ4 ４．３５ｇ（０．０２５ｍｏｌ）に超純水７５ｃｍ3を加えて混合した（この時のｐＨは約１２．５）。この水分散液にＦｅＳＯ4・７Ｈ2Ｏ６．９５ｇ（０．０２５ｍｏｌ）を添加し、混合した。得られた混合液をオートクレーブに投入し、１５０℃で１６ｈｒ水熱反応を行った。反応液をろ過後、凍結乾燥し、平均粒径５０ｎｍの球状一次粒子を得た。かかる球状一次粒子のＳＥＭ像を図１に示す。
なお、図１より、結晶子の粒径は２６ｎｍであることが確認された。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
[Example 1]
LiOH.H 2 O 4.20 g (0.1 mol), Na 4 SiO 4 .nH 2 O 6.99 g (0.025 mol), Na 2 S 2 O 4 4.35 g (0.025 mol) and ultrapure water 75 cm 3 was added and mixed (the pH at this time was about 12.5). To this aqueous dispersion, 6.95 g (0.025 mol) of FeSO 4 .7H 2 O was added and mixed. The obtained mixed liquid was put into an autoclave and subjected to a hydrothermal reaction at 150 ° C. for 16 hours. The reaction solution was filtered and then lyophilized to obtain spherical primary particles having an average particle size of 50 nm. An SEM image of such spherical primary particles is shown in FIG.
In addition, from FIG. 1, it was confirmed that the particle size of a crystallite is 26 nm.

次いで、得られた一次粒子１００ｇにグルコース（６０％水溶液）４５ｇ、及び超純水１００ｇを加え、スラリーを調整した。得られたスラリーの一次粒子の含有量は５０ｗｔ％であった。そして、噴霧乾燥装置（４流体ノズルを備えたマイクロミストドライヤー：藤崎電気（株）製）を用い、得られたスラリーを造粒した後、還元雰囲気下で６００℃で１ｈｒ焼成して、平均粒径１５μｍの二次粒子を作製した。かかる二次粒子のＳＥＭ像を図２に、二次粒子の一部のＴＥＭ像を図３に示す。なお、図３より、一次粒子及び二次粒子の表面に形成されたカーボン層の厚みは、２．５ｎｍであることが確認された。   Next, 45 g of glucose (60% aqueous solution) and 100 g of ultrapure water were added to 100 g of the obtained primary particles to prepare a slurry. The content of primary particles of the obtained slurry was 50 wt%. And after granulating the obtained slurry using a spray dryer (micro mist dryer equipped with a four-fluid nozzle: manufactured by Fujisaki Electric Co., Ltd.), it was calcined at 600 ° C. for 1 hour in a reducing atmosphere to obtain an average particle size. Secondary particles having a diameter of 15 μm were prepared. FIG. 2 shows an SEM image of such secondary particles, and FIG. 3 shows a TEM image of a part of the secondary particles. In addition, from FIG. 3, it was confirmed that the thickness of the carbon layer formed in the surface of a primary particle and a secondary particle is 2.5 nm.

［充放電試験］
実施例１で得られた二次粒子を用い、リチウムイオン二次電池の正極を作製した。実施例１で得られた二次粒子、ケッチェンブラック（導電剤）、ポリフッ化ビニリデン（粘結剤）を重量比７５：１５：１０の配合割合で混合し、これにＮ−メチル−２−ピロリドンを加えて充分混練し、正極スラリーを調製した。正極スラリーを厚さ２０μｍのアルミニウム箔からなる集電体に塗工機を用いて塗布し、８０℃で１２時間の真空乾燥を行った。その後、φ１４ｍｍの円盤状に打ち抜いてハンドプレスを用いて１６ＭＰａで２分間プレスし、正極とした。 [Charge / discharge test]
Using the secondary particles obtained in Example 1, a positive electrode of a lithium ion secondary battery was produced. The secondary particles obtained in Example 1, ketjen black (conductive agent), and polyvinylidene fluoride (binding agent) were mixed at a weight ratio of 75:15:10, and this was mixed with N-methyl-2- Pyrrolidone was added and sufficiently kneaded to prepare a positive electrode slurry. The positive electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a positive electrode.

次いで、上記の正極を用いてコイン型リチウムイオン二次電池を構築した。負極には、φ１５ｍｍに打ち抜いたリチウム箔を用いた。電解液には、エチレンカーボネート及びエチルメチルカーボネートを体積比１：１の割合で混合した混合溶媒に、ＬＩＰＦ6を１ｍｏｌ／ｌの濃度で溶解したものを用いた。セパレータには、ポリプロピレンなどの高分子多孔フィルムなど、公知のものを用いた。これらの電池部品を露点が−５０℃以下の雰囲気で常法により組み込み収容し、コイン型リチウム二次電池（ＣＲ−２０３２）を製造した。 Next, a coin-type lithium ion secondary battery was constructed using the positive electrode. A lithium foil punched to φ15 mm was used for the negative electrode. As the electrolytic solution, a solution obtained by dissolving LIPF 6 at a concentration of 1 mol / l in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 1: 1 was used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type lithium secondary battery (CR-2032).

製造したリチウムイオン二次電池を用いて定電流密度での充放電を４サイクル行った。このときの充電条件は電流０．１ＣＡ（３３ｍＡ／ｇ）、電圧４．５Ｖの定電流定電圧充電とし、放電条件は電流０．１ＣＡ、終止電圧１．５Ｖの定電流放電とした。温度は全て３０℃とした。実施例１の正極材で構築した電池の４サイクル目の充放電曲線を図４に示す。   Using the manufactured lithium ion secondary battery, charging / discharging at a constant current density was performed 4 cycles. The charging conditions at this time were constant current and constant voltage charging with a current of 0.1 CA (33 mA / g) and a voltage of 4.5 V, and the discharging conditions were constant current discharging with a current of 0.1 CA and a final voltage of 1.5 V. All temperatures were 30 ° C. FIG. 4 shows a charge / discharge curve of the fourth cycle of the battery constructed with the positive electrode material of Example 1.

図１〜３より、非常に微細で球状を呈した一次粒子が得られ、これら粒子同士が凝集しながら担持されたカーボンにより接合されて、１〜１００μｍの範囲内にある平均粒径を有する二次粒子を形成していることがわかる。また、図４より、実施例１で得られた正極活物質を用いたリチウムイオン電池は、優れた電池物性を有することがわかる。   1-3, very fine and spherical primary particles are obtained, and these particles are joined together by agglomerated carbon and have an average particle diameter in the range of 1 to 100 μm. It can be seen that secondary particles are formed. Further, FIG. 4 shows that the lithium ion battery using the positive electrode active material obtained in Example 1 has excellent battery properties.

Claims (4)

Ｌｉ2ＭＳｉＯ4（式中、ＭはＦｅ、Ｎｉ、Ｃｏ又はＭｎから選ばれる１種又は２種以上を示す）で表されるオリビン型シリケート化合物を含有し、
オリビン型シリケート化合物が、平均粒径２０〜１００ｎｍの球状一次粒子が凝集してなる平均粒径１〜１００μｍの二次粒子を有することを特徴とする、リチウムイオン電池用正極活物質。 Containing an olivine-type silicate compound represented by Li 2 MSiO 4 (wherein M represents one or more selected from Fe, Ni, Co or Mn),
A positive electrode active material for a lithium ion battery, wherein the olivine-type silicate compound has secondary particles having an average particle diameter of 1 to 100 µm formed by agglomerating spherical primary particles having an average particle diameter of 20 to 100 nm. 球状一次粒子及び二次粒子の表面に、１〜３ｎｍ厚のカーボン層が形成されてなる請求項１に記載のリチウムイオン電池用正極活物質。   The positive electrode active material for a lithium ion battery according to claim 1, wherein a carbon layer having a thickness of 1 to 3 nm is formed on the surfaces of the spherical primary particles and secondary particles. Ｌｉ2ＭＳｉＯ4が、Ｌｉ2ＦｅＳｉＯ4である請求項１又は２に記載のリチウムイオン電池用正極活物質。 The positive electrode active material for a lithium ion battery according to claim 1, wherein Li 2 MSiO 4 is Li 2 FeSiO 4 . 請求項３に記載のリチウムイオン電池用正極活物質を含む正極を有するリチウムイオン電池。   The lithium ion battery which has a positive electrode containing the positive electrode active material for lithium ion batteries of Claim 3.
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