JP6427312B2 - Positive electrode active material for lithium ion battery, positive electrode material for lithium ion battery, positive electrode for lithium ion battery, lithium ion battery and method for producing positive electrode active material for lithium ion battery - Google Patents
Positive electrode active material for lithium ion battery, positive electrode material for lithium ion battery, positive electrode for lithium ion battery, lithium ion battery and method for producing positive electrode active material for lithium ion battery Download PDFInfo
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- JP6427312B2 JP6427312B2 JP2013210258A JP2013210258A JP6427312B2 JP 6427312 B2 JP6427312 B2 JP 6427312B2 JP 2013210258 A JP2013210258 A JP 2013210258A JP 2013210258 A JP2013210258 A JP 2013210258A JP 6427312 B2 JP6427312 B2 JP 6427312B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Description
本発明は、リチウムイオン電池用正極活物質、リチウムイオン電池用正極材料、リチウムイオン電池用正極、およびリチウムイオン電池に関する。 The present invention relates to a positive electrode active material for lithium ion batteries, a positive electrode material for lithium ion batteries, a positive electrode for lithium ion batteries, and a lithium ion battery.
リチウムイオン電池は、一般的に、携帯電話やノートパソコンなどの小型携帯機器の電源として使用されている。また、最近では小型携帯機器以外に、電気自動車や電力貯蔵などの電源としてもリチウムイオン電池は使用され始めている。 Lithium ion batteries are generally used as a power source for small portable devices such as mobile phones and laptop computers. Also, recently, in addition to small portable devices, lithium ion batteries have also begun to be used as power sources for electric vehicles and power storage.
リチウムイオン電池用正極活物質として、酸化物系や硫化物系の正極活物質が知られている。硫化物系の正極活物質は、高容量のリチウムイオン電池が得られることから、酸化物系に代わる正極活物質として研究が進められている（例えば、特許文献１〜２）。 As positive electrode active materials for lithium ion batteries, oxide-based and sulfide-based positive electrode active materials are known. The sulfide-based positive electrode active material is being studied as a positive electrode active material to replace an oxide-based material because a high capacity lithium ion battery can be obtained (for example, Patent Documents 1 and 2).
ところが、硫化物系の正極活物質は、大きな理論容量を有しているものの、充放電に伴う体積変化が大きく、酸化物系の正極活物質に比べてサイクル特性が劣っていた。そのため、硫化物系の活物質は、リチウムイオン電池用正極活物質としてはまだまだ満足するものではなかった。 However, although the sulfide-based positive electrode active material has a large theoretical capacity, the volume change due to charge and discharge is large, and the cycle characteristics are inferior to the oxide-based positive electrode active material. Therefore, the sulfide-based active material is not yet satisfactory as a positive electrode active material for lithium ion batteries.
本発明者らは、サイクル特性に優れる、硫化物系のリチウムイオン電池用正極活物質を提供するため鋭意検討した。その結果、構成元素として、Ｌｉ、Ｍｏ、およびＳを含む硫化物系の材料がサイクル特性に優れることを見出し、本発明に至った。 The present inventors diligently studied to provide a sulfide-based positive electrode active material for a lithium ion battery excellent in cycle characteristics. As a result, it has been found that sulfide-based materials containing Li, Mo, and S as constituent elements have excellent cycle characteristics, and the present invention has been achieved.
本発明によれば、
構成元素として、Ｌｉ、Ｍｏ、およびＳのみを含み、かつ、充放電によりリチウムイオンを吸蔵・放出することが可能なＬｉ−Ｍｏ−Ｓ化合物を含み、
前記Ｌｉ−Ｍｏ−Ｓ化合物は、非晶質で、かつ、微粒子状であり、
前記Ｌｉ−Ｍｏ−Ｓ化合物中の前記Ｍｏの含有量に対する前記Ｌｉの含有量のモル比（Ｌｉ／Ｍｏ）が２以上２０以下であり、前記Ｍｏの含有量に対する前記Ｓの含有量のモル比（Ｓ／Ｍｏ）が３以上１３以下であり、
レーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径ｄ５０が０．５μｍ以上２０μｍ以下であり、
前記Ｌｉ−Ｍｏ−Ｓ化合物は、ＭｏＳ ２ およびＬｉ ２ Ｓのメカノケミカル処理物である、リチウムイオン電池用正極活物質が提供される。
また、本発明によれば、
構成元素として、Ｌｉ、Ｍｏ、およびＳのみを含み、かつ、充放電によりリチウムイオンを吸蔵・放出することが可能なＬｉ−Ｍｏ−Ｓ化合物を含み、
前記Ｌｉ−Ｍｏ−Ｓ化合物は、非晶質で、かつ、微粒子状であり、
前記Ｌｉ−Ｍｏ−Ｓ化合物中の前記Ｍｏの含有量に対する前記Ｌｉの含有量のモル比（Ｌｉ／Ｍｏ）が２以上２０以下であり、前記Ｍｏの含有量に対する前記Ｓの含有量のモル比（Ｓ／Ｍｏ）が３以上１３以下であり、
レーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径ｄ ５０ が０．５μｍ以上２０μｍ以下であり、
前記Ｌｉ−Ｍｏ−Ｓ化合物は、ＭｏＳ ２ 、Ｌｉ ２ Ｓ、およびＳのメカノケミカル処理物である、リチウムイオン電池用正極活物質が提供される。
According to the invention
As a constituent element, it contains only Li, Mo, and S, and contains a Li-Mo-S compound capable of absorbing and releasing lithium ions by charge and discharge,
The Li-Mo-S compound is amorphous and particulate.
The molar ratio (Li / Mo) of the content of Li to the content of Mo in the Li-Mo-S compound is 2 or more and 20 or less, and the molar ratio of the content of S to the content of Mo (S / Mo) is 3 or more and 13 or less,
Ri average particle diameter d 50 of Der least 20μm or less 0.5μm in weight particle size distribution by a laser diffraction scattering particle size distribution measuring method,
The Li-Mo-S compound is a mechanochemically processed product of MoS 2 and Li 2 S, and provides a positive electrode active material for a lithium ion battery.
Moreover, according to the present invention,
As a constituent element, it contains only Li, Mo, and S, and contains a Li-Mo-S compound capable of absorbing and releasing lithium ions by charge and discharge,
The Li-Mo-S compound is amorphous and particulate.
The molar ratio (Li / Mo) of the content of Li to the content of Mo in the Li-Mo-S compound is 2 or more and 20 or less, and the molar ratio of the content of S to the content of Mo (S / Mo) is 3 or more and 13 or less,
The average particle diameter d 50 in the weight-based particle size distribution by the laser diffraction / scattering particle size distribution measurement method is from 0.5 μm to 20 μm,
The Li-MoS compounds are mechanochemical treatment of MoS 2, Li 2 S, and S, the positive electrode active material is provided for a lithium ion battery.
さらに、本発明によれば、
上記本発明のリチウムイオン電池用正極活物質を主成分として含む、リチウムイオン電池用正極材料が提供される。
Furthermore, according to the invention,
The positive electrode material for lithium ion batteries which contains the said positive electrode active material for lithium ion batteries of this invention as a main component is provided.
さらに、本発明によれば、
上記本発明のリチウムイオン電池用正極材料からなる正極活物質層を集電体の表面に形成してなる、リチウムイオン電池用正極が提供される。
Furthermore, according to the invention,
There is provided a positive electrode for a lithium ion battery, wherein the positive electrode active material layer comprising the positive electrode material for a lithium ion battery of the present invention is formed on the surface of a current collector.
さらに、本発明によれば、
上記本発明のリチウムイオン電池用正極と、電解質層と、負極とを備えた、リチウムイオン電池が提供される。
Furthermore, according to the invention,
The lithium ion battery provided with the said positive electrode for lithium ion batteries of this invention, an electrolyte layer, and a negative electrode is provided.
本発明によれば、サイクル特性に優れるリチウムイオン電池を得ることができる硫化物系のリチウムイオン電池用正極活物質、これを含む正極材料、および正極並びにサイクル特性に優れるリチウムイオン電池を提供することができる。 According to the present invention, it is possible to provide a positive electrode active material for a sulfide-based lithium ion battery capable of obtaining a lithium ion battery excellent in cycle characteristics, a positive electrode material containing the same, and a lithium ion battery excellent in cathode and cycle characteristics Can.
以下に、本発明の実施形態について、図面を用いて説明する。図は概略図であり、実際の寸法比率とは必ずしも一致していない。なお、本実施形態では特に断りがなければ、正極活物質を含む層を正極活物質層と呼び、集電体上に正極活物質層を形成させたものを正極と呼ぶ。また、負極活物質を含む層を負極活物質層と呼び、集電体上に負極活物質層を形成させたものを負極と呼ぶ。 Hereinafter, embodiments of the present invention will be described using the drawings. The figure is a schematic view and does not necessarily match the actual dimensional ratio. In the present embodiment, unless otherwise specified, a layer containing a positive electrode active material is referred to as a positive electrode active material layer, and a layer in which a positive electrode active material layer is formed on a current collector is referred to as a positive electrode. Further, a layer containing a negative electrode active material is called a negative electrode active material layer, and a layer in which a negative electrode active material layer is formed on a current collector is called a negative electrode.
［リチウムイオン電池用正極活物質］
はじめに、本実施形態のリチウムイオン電池用正極活物質について説明する。
本実施形態のリチウムイオン電池用正極活物質（以下、正極活物質とも呼ぶ。）は、構成元素として、Ｌｉ、Ｍｏ、およびＳを含んでいる。
[Positive electrode active material for lithium ion battery]
First, the positive electrode active material for a lithium ion battery of the present embodiment will be described.
The positive electrode active material for a lithium ion battery of the present embodiment (hereinafter also referred to as a positive electrode active material) contains Li, Mo, and S as constituent elements.
本実施形態の正極活物質は、Ｌｉ、Ｍｏ、およびＳを必須元素として含む化合物からなる。本実施形態の正極活物質を用いると、サイクル特性に優れるリチウムイオン電池を得ることができる。この理由については必ずしも明らかではないが、以下の理由が推察される。
まず詳細は後述するが、本実施形態の正極活物質は、通常は原料であるＭｏＳ２およびＬｉ２Ｓを混合することにより得ることができる。ここで、原料であるＭｏＳ２は、リチウムイオンのインターカレーションによる体積収縮が小さい材料である。このＭｏＳ２にＬｉ２Ｓを混合し、Ｓの量を高めると、ＭｏＳ２の結晶構造からなるドメインが微細化し、非晶質のＬｉ−Ｍｏ−Ｓ化合物が生成することでリチウムイオンが出入りするサイトが広がるとともにリチウムイオンが出入りするサイト数が増加すると考えられる。そしてその結果として、本実施形態の正極活物質はインターカレーションによる体積収縮がより一層小さい材料となり、優れたサイクル特性を実現できていると推察される。
The positive electrode active material of the present embodiment is made of a compound containing Li, Mo and S as essential elements. By using the positive electrode active material of the present embodiment, a lithium ion battery excellent in cycle characteristics can be obtained. Although the reasons for this are not necessarily clear, the following reasons are inferred.
First, although the details will be described later, the positive electrode active material of the present embodiment can be generally obtained by mixing MoS 2 and Li 2 S, which are raw materials. Here, MoS 2 which is a raw material is a material having a small volume contraction due to lithium ion intercalation. When Li 2 S is mixed with this MoS 2 and the amount of S is increased, the domain consisting of the crystal structure of MoS 2 becomes finer, and an amorphous Li-Mo-S compound is formed to allow lithium ions to enter and exit. It is considered that the number of sites where lithium ions enter and leave increases as the sites spread. And as a result, it is inferred that the positive electrode active material of the present embodiment is a material whose volume contraction due to intercalation is further smaller, and that excellent cycle characteristics can be realized.
また、本実施形態のリチウムイオン電池用正極活物質は、上記Ｍｏの含有量に対する上記Ｌｉの含有量のモル比（Ｌｉ／Ｍｏ）が好ましくは２以上２０以下であり、より好ましくは４以上１９以下であり、さらに好ましくは５以上１７以下であり、特に好ましくは６以上１４以下である。また、上記Ｍｏの含有量に対する上記Ｓの含有量のモル比（Ｓ／Ｍｏ）が、好ましくは３以上１３以下であり、より好ましくは４以上１２以下であり、さらに好ましくは５以上１０以下であり、特に好ましくは６以上９以下である。
Ｌｉ／ＭｏおよびＳ／Ｍｏを上記範囲内とすることにより、充放電容量（ｍＡｈ／ｇ）をより一層向上させることができる。
ここで、本実施形態の正極活物質中のＬｉ、Ｍｏ、およびＳの含有量は、例えば、ＩＣＰ発光分光分析により求めることができる。
The positive electrode active material for a lithium ion battery according to this embodiment preferably has a molar ratio (Li / Mo) of the content of Li to the content of Mo of 2 to 20, and more preferably 4 to 19 Or less, more preferably 5 or more and 17 or less, and particularly preferably 6 or more and 14 or less. In addition, the molar ratio (S / Mo) of the content of S to the content of Mo is preferably 3 or more and 13 or less, more preferably 4 or more and 12 or less, and still more preferably 5 or more and 10 or less. And particularly preferably 6 or more and 9 or less.
By making Li / Mo and S / Mo within the above ranges, the charge and discharge capacity (mAh / g) can be further improved.
Here, the content of Li, Mo, and S in the positive electrode active material of the present embodiment can be determined, for example, by ICP emission spectral analysis.
また、本実施形態のリチウムイオン電池用正極活物質は特に限定されないが、レーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径ｄ５０が、好ましくは０．５μｍ以上２０μｍ以下であり、より好ましくは１μｍ以上１０μｍ以下である。
正極活物質の平均粒子径ｄ５０を上記範囲内とすることにより、良好なハンドリング性を維持すると共に、より一層高密度の正極を作製することができる。
The positive electrode active material for a lithium ion battery according to this embodiment is not particularly limited, but the average particle diameter d 50 in the weight-based particle size distribution by laser diffraction / scattering type particle size distribution measurement is preferably 0.5 μm to 20 μm. And more preferably 1 μm or more and 10 μm or less.
By setting the average particle diameter d 50 of the positive electrode active material in the above range, it is possible to maintain a good handling property and to produce a still higher density positive electrode.
また、本実施形態のリチウムイオン電池用正極活物質は特に限定されないが、窒素吸着におけるＢＥＴ３点法による比表面積が、好ましくは０．１ｍ２／ｇ以上４ｍ２／ｇ以下であり、より好ましくは０．２ｍ２／ｇ以上２ｍ２／ｇ以下である。
窒素吸着におけるＢＥＴ３点法による比表面積が上記上限値以下であることにより、正極活物質と電解質との不可逆的な反応をより一層抑制することができる。
また、窒素吸着におけるＢＥＴ３点法による比表面積を上記下限値以上であることにより、電解質の正極活物質への浸透性を向上させることができる。
The positive electrode active material for lithium ion batteries of the present embodiment is not particularly limited, but the specific surface area according to the BET three-point method in nitrogen adsorption is preferably 0.1 m 2 / g or more and 4 m 2 / g or less, more preferably 0.2 m 2 / g or more and 2 m 2 / g or less.
When the specific surface area according to the BET three-point method in nitrogen adsorption is not more than the above upper limit value, irreversible reaction between the positive electrode active material and the electrolyte can be further suppressed.
Moreover, the permeability to the positive electrode active material of an electrolyte can be improved by making the specific surface area by BET 3 point method in nitrogen adsorption more than the said lower limit.
［リチウムイオン電池用正極活物質の製造方法］
つづいて、本実施形態のリチウムイオン電池用正極活物質の製造方法について説明する。
本実施形態の正極活物質は、例えば、原料であるＭｏＳ２、Ｌｉ２Ｓ、必要に応じてＳ（硫黄）を粉砕混合することにより得ることができる。以下、具体的に説明する。
[Method of producing positive electrode active material for lithium ion battery]
It continues and demonstrates the manufacturing method of the positive electrode active material for lithium ion batteries of this embodiment.
The positive electrode active material of the present embodiment can be obtained, for example, by pulverizing and mixing the raw materials MoS 2 and Li 2 S and, if necessary, S (sulfur). The details will be described below.
はじめに、Ｌｉ２Ｓに対するＭｏＳ２の反応モル比（ＭｏＳ２／Ｌｉ２Ｓ）が好ましくは０．０５以上１．２以下、より好ましくは０．１０以上０．５０以下、特に好ましくは０．１２以上０．３５以下となるように、ＭｏＳ２およびＬｉ２Ｓを混合する。得られる正極活物質中のＳの量を高めたい場合は、さらにＳ（硫黄）を添加してもよい。
ここで、Ｌｉ２Ｓに対するＭｏＳ２の混合モル比が、通常はＬｉ２Ｓに対するＭｏＳ２の反応モル比となる。本実施形態の混合モル比は、例えば、ＩＣＰ発光分光分析により求めることができるが、通常は仕込みの重量比から算出できる。
First, the reaction molar ratio of MoS 2 with respect to Li 2 S (MoS 2 / Li 2 S) is preferably 0.05 to 1.2, more preferably 0.10 to 0.50, particularly preferably 0.12 MoS 2 and Li 2 S are mixed so as to be 0.35 or less. When it is desired to increase the amount of S in the obtained positive electrode active material, S (sulfur) may be further added.
Here, the mixing molar ratio of MoS 2 with respect to Li 2 S, usually a reaction molar ratio of MoS 2 with respect to Li 2 S. The mixing molar ratio of the present embodiment can be determined, for example, by ICP emission spectrometry, but can usually be calculated from the weight ratio of preparation.
ＭｏＳ２およびＬｉ２Ｓを粉砕混合する方法としてはＭｏＳ２およびＬｉ２Ｓを均一に粉砕混合できる混合方法であれば特に限定されないが、例えば、非活性雰囲気下で撹拌またはメカノケミカル処理によりおこなうことができる。非活性雰囲気下でメカノケミカル処理によりおこなうことが好ましい。メカノケミカル処理を用いると、ＭｏＳ２とＬｉ２Ｓとを微粒子状に粉砕しながら混合することができるため、ＭｏＳ２とＬｉ２Ｓとの接触面積を大きくすることができる。それにより、ＭｏＳ２とＬｉ２Ｓとの反応を促進することができるため、より一層効率良く本実施形態の正極活物質を得ることができる。 MoS 2 and Li 2 as a method S mixing pulverization is not particularly limited as long as the mixing method capable of uniformly pulverized and mixed MoS 2 and Li 2 S, for example, be carried out by stirring or mechanochemical treatment under inert atmosphere Can. It is preferable to carry out by mechanochemical treatment in a non-active atmosphere. When mechanochemical treatment is used, MoS 2 and Li 2 S can be mixed while being pulverized into fine particles, so the contact area between MoS 2 and Li 2 S can be increased. Thereby, since the reaction of MoS 2 and Li 2 S can be promoted, the positive electrode active material of the present embodiment can be obtained more efficiently.
ここで、メカノケミカル処理による混合方法とは、混合対象に、せん断力、衝突力または遠心力のような機械的エネルギーを加えつつ混合する方法である。メカノケミカル処理による混合をおこなう装置としては、ボールミル、ビーズミル、振動ミルなどの粉砕・分散機が挙げられる。 Here, the mixing method by mechanochemical treatment is a method of mixing while adding mechanical energy such as shear force, collision force or centrifugal force to the object to be mixed. As an apparatus which performs mixing by mechanochemical processing, grinding | pulverization * dispersers, such as a ball mill, a bead mill, a vibration mill, are mentioned.
また、上記非活性雰囲気下とは、１〜１０−５Ｐａの真空雰囲気下または不活性ガス雰囲気下のことである。上記非活性雰囲気下では、水分の接触を避けるために露点が−５０℃以下であることが好ましく、−６０℃以下であることがより好ましい。上記不活性ガス雰囲気下とは、アルゴンガス、ヘリウムガス、窒素ガスなどの不活性ガスの雰囲気下のことである。これらの不活性ガスは、製品への不純物の混入を防止するために、高純度である程好ましい。混合系への不活性ガスの導入方法としては、混合系内が不活性ガス雰囲気で満たされる方法であれば特に限定されないが、不活性ガスをパージする方法、不活性ガスを一定量導入し続ける方法などが挙げられる。 Moreover, under the said non-active atmosphere is a vacuum atmosphere of 1-10 < -5 > Pa, or an inert gas atmosphere. Under the non-active atmosphere, the dew point is preferably −50 ° C. or less, more preferably −60 ° C. or less, in order to avoid contact with water. The inert gas atmosphere is an atmosphere of an inert gas such as argon gas, helium gas, nitrogen gas and the like. These inert gases are preferably as high in purity as possible to prevent contamination of the product with impurities. The method of introducing the inert gas into the mixed system is not particularly limited as long as the mixed system is filled with an inert gas atmosphere, but a method of purging the inert gas, the constant amount of the inert gas is continued to be introduced Methods etc.
また、ＭｏＳ２およびＬｉ２Ｓを混合する時に、ヘキサン、トルエン、またはキシレンなどの非プロトン性有機溶媒を添加して、溶媒に各原料を分散させた状態で混合してもよい。こうすることにより、より効率良く混合することができる。 Moreover, when mixing MoS 2 and Li 2 S, an aprotic organic solvent such as hexane, toluene, or xylene may be added, and the materials may be mixed in the solvent in a dispersed state. By doing this, mixing can be performed more efficiently.
ＭｏＳ２およびＬｉ２Ｓを粉砕混合するときの攪拌速度や処理時間、温度、反応圧力、混合物に加えられる重力加速度などの混合条件は、混合物の処理量によって適宜決定することができる。 Mixing conditions such as stirring speed, processing time, temperature, reaction pressure, gravitational acceleration applied to the mixture when grinding and mixing MoS 2 and Li 2 S can be appropriately determined depending on the amount of the mixture to be processed.
（Ｌｉ２Ｓ）
本実施形態のＬｉ２Ｓとしては特に限定されず、市販されているＬｉ２Ｓを使用してもよいし、例えば水酸化リチウムと硫化水素との反応により得られるＬｉ２Ｓを使用してもよい。高純度な正極活物質を得る観点から、不純物の少ないＬｉ２Ｓを使用することが好ましい。
(Li 2 S)
There is no particular limitation on Li 2 S in the present embodiment, and commercially available Li 2 S may be used, for example, Li 2 S obtained by the reaction of lithium hydroxide and hydrogen sulfide may also be used. Good. From the viewpoint of obtaining a high purity positive electrode active material, it is preferable to use Li 2 S with few impurities.
本実施形態のＬｉ２Ｓのレーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径ｄ５０は、好ましくは平均粒子径ｄ５０が２０μｍ以下であり、より好ましくは１０μｍ以下であり、特に好ましくは５μｍ以下である。平均粒子径ｄ５０を上記上限値以下とすることにより、ＭｏＳ２とＬｉ２Ｓとの接触面積を大きくすることができる。これにより、ＭｏＳ２とＬｉ２Ｓとの反応を促進することができるため、より一層効率良く本実施形態の正極活物質を得ることができる。
また、Ｌｉ２Ｓの平均粒子径ｄ５０の下限値は特に限定されないが、取り扱い性の観点から、例えば０．１μｍ以上である。
The average particle size d 50 in the weight particle size distribution by a laser diffraction scattering particle size distribution measurement method of Li 2 S of this embodiment is preferably not average particle size d 50 20 [mu] m or less, more preferably 10μm or less, Particularly preferably, it is 5 μm or less. By setting the average particle diameter d 50 to the upper limit value or less, the contact area between MoS 2 and Li 2 S can be increased. Thereby, since the reaction of MoS 2 and Li 2 S can be promoted, the positive electrode active material of the present embodiment can be obtained more efficiently.
The lower limit of the average particle diameter d 50 of Li 2 S is not particularly limited, but is, for example, 0.1 μm or more from the viewpoint of handleability.
（ＭｏＳ２）
本実施形態のＭｏＳ２としては特に限定されず、市販されているＭｏＳ２を使用することができる。高純度な正極活物質を得る観点から、不純物の少ないＭｏＳ２を使用することが好ましい。
(MoS 2 )
Is not particularly limited as MoS 2 of the present embodiment, it is possible to use a MoS 2, which is commercially available. From the viewpoint of obtaining a high purity positive electrode active material, it is preferable to use MoS 2 with few impurities.
本実施形態のＭｏＳ２のレーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径ｄ５０は、好ましくは平均粒子径ｄ５０が２０ｍ以下であり、より好ましくは１０μｍ以下である。平均粒子径ｄ５０を上記上限値以下とすることにより、ＭｏＳ２とＬｉ２Ｓとの接触面積を大きくすることができる。それにより、ＭｏＳ２とＬｉ２Ｓとの反応を促進することができるため、より一層効率良く本実施形態の正極活物質を得ることができる。
また、ＭｏＳ２の平均粒子径ｄ５０の下限値は特に限定されないが、取り扱い性の観点から、例えば１μｍ以上である。
The average particle size d 50 in the weight particle size distribution by laser diffraction scattering of MoS 2 particle size distribution measurement method of this embodiment is preferably not more than an average particle size d 50 20 m, more preferably 10μm or less. By setting the average particle diameter d 50 to the upper limit value or less, the contact area between MoS 2 and Li 2 S can be increased. Thereby, since the reaction of MoS 2 and Li 2 S can be promoted, the positive electrode active material of the present embodiment can be obtained more efficiently.
The lower limit value of the average particle diameter d 50 of MoS 2 is not particularly limited, but is, for example, 1 μm or more from the viewpoint of handleability.
（Ｓ）
本実施形態のＳ（硫黄）としては特に限定されず、市販されている硫黄を使用することができる。高純度な正極活物質を得る観点から、不純物の少ない硫黄を使用することが好ましい。
(S)
It does not specifically limit as S (sulfur) of this embodiment, Sulfur marketed can be used. From the viewpoint of obtaining a high purity positive electrode active material, it is preferable to use sulfur with few impurities.
このような製造方法により、本実施形態の正極活物質を得ることができる。 The positive electrode active material of the present embodiment can be obtained by such a manufacturing method.
本実施形態の正極活物質の製造方法では、必要に応じて、得られた正極活物質を粉砕、分級、または造粒する工程をさらにおこなってもよい。例えば、粉砕により微粒子化し、その後、分級操作や造粒操作によって粒子径を調整することにより、所望の粒子径を有する正極活物質を得ることができる。上記粉砕方法としては特に限定されず、乳鉢、回転ミル、コーヒーミルなど公知の粉砕方法を用いることができる。また、上記分級方法としては特に限定されず、篩など公知の方法を用いることができる。
これらの粉砕または分級は、空気中の水分との接触を防ぐことができる点から、不活性ガス雰囲気下または真空雰囲気下で行うことが好ましい。
また、粉砕、分級、または造粒する工程は、原料であるＭｏＳ２、Ｌｉ２ＳおよびＳに対しておこなってもよいし、上記混合物に対しておこなってもよい。
In the method of manufacturing the positive electrode active material of the present embodiment, a step of grinding, classifying, or granulating the obtained positive electrode active material may be further performed as necessary. For example, it is possible to obtain a positive electrode active material having a desired particle size by pulverizing into fine particles and thereafter adjusting the particle size by classification operation or granulation operation. It does not specifically limit as said grinding method, Well-known grinding methods, such as a mortar, a rotary mill, a coffee mill, can be used. Moreover, it does not specifically limit as said classification method, Well-known methods, such as a sieve, can be used.
It is preferable to carry out such pulverization or classification under an inert gas atmosphere or a vacuum atmosphere in that it can prevent contact with moisture in the air.
In addition, the steps of grinding, classification, or granulation may be performed on the raw materials MoS 2 , Li 2 S, and S, or may be performed on the above mixture.
本実施形態の正極活物質を得るためには、上記の各工程を適切に調整することが重要である。ただし、本実施形態の正極活物質の製造方法は、上記のような方法には限定されず、種々の条件を適切に調整することにより、本実施形態の正極活物質を得ることができる。 In order to obtain the positive electrode active material of the present embodiment, it is important to properly adjust each of the above steps. However, the method of manufacturing the positive electrode active material of the present embodiment is not limited to the method as described above, and the positive electrode active material of the present embodiment can be obtained by appropriately adjusting various conditions.
本実施形態の正極活物質は高い充放電容量を有し、かつ、サイクル特性に優れているため、リチウムイオン電池用の正極活物質として有用である。 Since the positive electrode active material of the present embodiment has high charge and discharge capacity and is excellent in cycle characteristics, it is useful as a positive electrode active material for lithium ion batteries.
［リチウムイオン電池用正極材料］
つぎに、本実施形態のリチウムイオン電池用正極材料について説明する。
本実施形態のリチウムイオン電池用正極材料（以下、正極材料とも呼ぶ。）は、本実施形態のリチウムイオン電池用正極活物質を主成分として含んでいる。そして、本実施形態の正極材料は特に限定されないが、本実施形態の正極活物質以外の成分として、例えば、バインダー、導電助剤、増粘剤、固体電解質、上述した本実施形態の正極活物質とは異なる種類の正極活物質などから選択される１種以上の材料を含んでもよい。
[Positive material for lithium ion battery]
Below, the positive electrode material for lithium ion batteries of this embodiment is demonstrated.
The positive electrode material for a lithium ion battery of the present embodiment (hereinafter also referred to as a positive electrode material) contains, as a main component, the positive electrode active material for a lithium ion battery of the present embodiment. And although the positive electrode material of this embodiment is not specifically limited, For example, a binder, a conductive support agent, a thickener, a solid electrolyte, the positive electrode active material of this embodiment mentioned above as components other than the positive electrode active material of this embodiment And at least one material selected from positive electrode active materials of different types.
（バインダー）
本実施形態の正極材料は、正極活物質同士および正極活物質と集電体とを結着させる役割をもつバインダーを含んでもよい。ただし、本実施形態の正極活物質は水と接触すると加水分解を起こすため、水溶性のポリビニルアルコール、ポリアクリル酸、カルボキシメチルセルロース、ポリテトラフルオロエチレン微粒子、スチレン・ブタジエン系ゴム微粒子などを水に分散したバインダーは適さない。
本実施形態のバインダーはリチウムイオン電池に通常使用されるバインダーの中で有機溶剤系バインダーであれば特に限定されないが、例えば、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリイミドなどが挙げられる。これらのバインダーは一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。
(binder)
The positive electrode material of the present embodiment may include a binder having a function of binding the positive electrode active materials to one another and the positive electrode active material and the current collector. However, since the positive electrode active material of the present embodiment causes hydrolysis when contacted with water, water-soluble polyvinyl alcohol, polyacrylic acid, carboxymethyl cellulose, polytetrafluoroethylene fine particles, styrene butadiene rubber fine particles, etc. are dispersed in water Binders are not suitable.
The binder in the present embodiment is not particularly limited as long as it is an organic solvent-based binder among binders generally used for lithium ion batteries, and examples thereof include polytetrafluoroethylene, polyvinylidene fluoride, polyimide and the like. These binders may be used alone or in a combination of two or more.
（増粘剤）
本実施形態の正極材料は、有機溶媒系バインダーを使用すると比較的粘性が得られ易いため通常は不要であるが、塗布に適したスラリーの流動性を調整する点から、増粘剤を含んでもよい。本実施形態の増粘剤としては膨潤性粘度鉱物のスクメタイト、ポリビニルカルボン酸アミドなどが挙げられる。これらの増粘剤は一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。
(Thickener)
The positive electrode material of the present embodiment is usually unnecessary because the use of an organic solvent-based binder makes it relatively easy to obtain viscosity, but it also contains a thickener in order to adjust the fluidity of the slurry suitable for application. Good. Examples of the thickener according to the present embodiment include squaveite of a swellable viscosity mineral and polyvinyl carboxylic acid amide. These thickeners may be used alone or in combination of two or more.
（導電助剤）
本実施形態の正極材料は、正極の導電性を向上させる観点から、導電助剤を含んでもよい。本実施形態の導電助剤としてはリチウムイオン電池に使用可能な通常の導電助剤であれば特に限定されないが、例えば、アセチレンブラック、ケチェンブラックなどのカーボンブラック、気相法炭素繊維などの炭素材料が挙げられる。
(Conduction agent)
The positive electrode material of the present embodiment may contain a conductive aid from the viewpoint of improving the conductivity of the positive electrode. The conductive support agent of the present embodiment is not particularly limited as long as it is a common conductive support agent usable for lithium ion batteries, but, for example, carbon such as acetylene black, carbon black such as ketjen black, and vapor grown carbon fiber Materials can be mentioned.
（固体電解質）
本実施形態の正極材料を全固体リチウムイオン電池用の正極に用いる場合は、本実施形態の正極材料は固体電解質を含んでいるのが好ましい。本実施形態の固体電解質としては、イオン伝導性および絶縁性を有するものであれば特に限定されないが、一般的に全固体リチウムイオン電池に用いられるものを用いることができる。例えば、硫化物固体電解質材料、酸化物固体電解質材料などを挙げることができる。これらの中でも、硫化物固体電解質材料が好ましい。これにより、本実施形態の正極活物質との界面抵抗が低下し、出力特性に優れた全固体リチウムイオン電池とすることができる。
(Solid electrolyte)
When the positive electrode material of the present embodiment is used as a positive electrode for an all solid lithium ion battery, the positive electrode material of the present embodiment preferably contains a solid electrolyte. The solid electrolyte of the present embodiment is not particularly limited as long as it has ion conductivity and insulating properties, and those generally used for all solid lithium ion batteries can be used. For example, a sulfide solid electrolyte material, an oxide solid electrolyte material, etc. can be mentioned. Among these, sulfide solid electrolyte materials are preferable. Thereby, the interface resistance with the positive electrode active material of the present embodiment is lowered, and an all solid lithium ion battery excellent in output characteristics can be obtained.
本実施形態の硫化物固体電解質材料としては、例えば、Ｌｉ２Ｓ−Ｐ２Ｓ５材料、Ｌｉ２Ｓ−ＳｉＳ２材料、Ｌｉ２Ｓ−ＧｅＳ２材料、Ｌｉ２Ｓ−Ａｌ２Ｓ３材料などが挙げられる。これらの中でも、リチウムイオン伝導性が優れており、製造方法が簡便である点から、Ｌｉ２Ｓ−Ｐ２Ｓ５材料が好ましい。 As a sulfide solid electrolyte material of the present embodiment, for example, Li 2 S-P 2 S 5 material, Li 2 S-SiS 2 material, Li 2 S-GeS 2 material, Li 2 S-Al 2 S 3 material, etc. Can be mentioned. Among these, the Li 2 S—P 2 S 5 material is preferable in terms of its excellent lithium ion conductivity and the simple production method.
（本実施形態の正極活物質とは異なる種類の正極活物質）
本実施形態の正極材料は、本発明の目的を損なわない範囲で、上述した本実施形態の正極活物質とは異なる種類の正極活物質を含んでもよい。本実施形態の正極活物質とは異なる種類の正極活物質としては特に限定されず一般的に公知のものを使用することができる。例えば、リチウムコバルト酸化物（ＬｉＣｏＯ２）、リチウムニッケル酸化物（ＬｉＮｉＯ２）、リチウムマンガン酸化物（ＬｉＭｎ２Ｏ４）などの複合酸化物；ポリアニリン、ポリピロールなどの導電性高分子；Ｌｉ２Ｓなどの硫化物；硫黄を用いることができる。
(Positive electrode active material of a type different from the positive electrode active material of the present embodiment)
The positive electrode material of the present embodiment may contain a positive electrode active material of a type different from the above-described positive electrode active material of the present embodiment, as long as the object of the present invention is not impaired. The type of positive electrode active material different from the positive electrode active material of the present embodiment is not particularly limited, and generally known materials can be used. For example, complex oxides such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ) and lithium manganese oxide (LiMn 2 O 4 ); conductive polymers such as polyaniline and polypyrrole; Li 2 S and the like Sulfides; sulfur can be used.
（各種材料の配合割合）
本実施形態のリチウムイオン電池用正極材料の各種材料の配合は、電池の使用用途などに応じて、適宜決定されるため特に限定されず、一般的に公知の情報に準じて設定することができる。
(Blending ratio of various materials)
The blending of various materials of the positive electrode material for lithium ion batteries of the present embodiment is not particularly limited because it is appropriately determined according to the use application of the battery and the like, and can be set according to generally known information. .
［リチウムイオン電池用正極］
つぎに、本実施形態の正極材料を含むリチウムイオン電池用正極について説明する。
本実施形態のリチウムイオン電池用正極は特に限定されないが、例えば、本実施形態の正極材料からなる正極活物質層をアルミなどの集電体の表面に形成することにより得られる。
[Positive electrode for lithium ion battery]
Below, the positive electrode for lithium ion batteries containing the positive electrode material of this embodiment is demonstrated.
The positive electrode for a lithium ion battery of the present embodiment is not particularly limited, but can be obtained, for example, by forming a positive electrode active material layer made of the positive electrode material of the present embodiment on the surface of a current collector such as aluminum.
本実施形態のリチウムイオン電池用正極の厚みや密度は、電池の使用用途などに応じて適宜決定されるため特に限定されず、一般的に公知の情報に準じて設定することができる。 The thickness and density of the positive electrode for a lithium ion battery according to the present embodiment are not particularly limited because they are appropriately determined in accordance with the use and the like of the battery, and can be set according to generally known information.
［リチウムイオン電池用正極の製造方法］
つぎに、本実施形態のリチウムイオン電池用正極の製造方法について説明する。
本実施形態のリチウムイオン電池用正極は特に限定されないが、一般的に公知の方法に準じて製造することができる。例えば、以下の（Ａ）および（Ｂ）工程を含んでいる。
（Ａ）正極スラリーを調製する工程
（Ｂ）得られた正極スラリーを集電体上に塗布することにより、正極活物質層を形成する工程
[Method of producing positive electrode for lithium ion battery]
Below, the manufacturing method of the positive electrode for lithium ion batteries of this embodiment is demonstrated.
The positive electrode for a lithium ion battery of the present embodiment is not particularly limited, but can be manufactured according to a generally known method. For example, the following (A) and (B) processes are included.
(A) Step of preparing positive electrode slurry (B) Step of forming positive electrode active material layer by applying the obtained positive electrode slurry on a current collector
＜正極スラリーを調製する工程＞
はじめに、（Ａ）正極スラリーを調製する工程について説明する。
本実施形態の正極スラリーの調製は一般的に公知の方法に準じておこなうことができるため特に限定されないが、例えば、本実施形態の正極活物質、必要に応じて、バインダー、増粘剤、導電助剤、電解質、本実施形態の正極活物質とは異なる種類の正極活物質などを混合機により混合して、溶剤に分散または溶解させることにより調製することができる。正極スラリー中の各材料の混合比は、電池の使用用途などに応じて適宜決定される。
混合機としては、ボールミル、プラネタリーミキサーなど公知のものが使用でき、特に限定されない。混合方法も特に限定されず、公知の方法に準じておこなうことができる。
<Step of Preparing Positive Electrode Slurry>
First, the step of preparing (A) the positive electrode slurry will be described.
Preparation of the positive electrode slurry of the present embodiment is not particularly limited because it can be carried out according to a generally known method, but, for example, the positive electrode active material of the present embodiment, if necessary, a binder, thickener, conductive An auxiliary agent, an electrolyte, a positive electrode active material of a type different from the positive electrode active material of this embodiment, and the like are mixed by a mixer, and the mixture can be prepared by dispersing or dissolving in a solvent. The mixing ratio of each material in the positive electrode slurry is appropriately determined depending on the application of the battery and the like.
As a mixer, a well-known thing, such as a ball mill and a planetary mixer, can be used, and it is not particularly limited. The mixing method is also not particularly limited, and may be carried out according to known methods.
＜正極活物質層を形成する工程＞
つづいて、（Ｂ）得られた正極スラリーを集電体上に塗布することにより、正極活物質層を形成する工程について説明する。
<Step of Forming Positive Electrode Active Material Layer>
Then, the process of forming a positive electrode active material layer is demonstrated by apply | coating the (B) obtained positive electrode slurry on a collector.
正極スラリーを集電体上に塗布する方法は、一般的に公知の方法を用いることができる。例えば、リバースロール法、ダイレクトロール法、ドクターブレード法、ナイフ法、エクストルージョン法、カーテン法、グラビア法、バー法、ディップ法、スクイーズ法などを挙げることができる。 As a method of applying the positive electrode slurry on the current collector, generally known methods can be used. For example, reverse roll method, direct roll method, doctor blade method, knife method, extrusion method, curtain method, gravure method, bar method, dip method, squeeze method etc. can be mentioned.
正極スラリーは、集電体の片面のみ塗布しても両面に塗布してもよい。塗布層の厚さ、長さや幅は、電池の大きさや用途に応じて、適宜決定することができる。
塗布した正極スラリーの乾燥方法は、一般的に公知の方法を用いることができる。
The positive electrode slurry may be coated on only one side or both sides of the current collector. The thickness, length and width of the coating layer can be appropriately determined according to the size and application of the battery.
A commonly known method can be used to dry the coated positive electrode slurry.
本実施形態の正極の製造に用いられる集電体としては特に限定されず、アルミニウム箔などリチウムイオン電池に使用可能な通常の集電体を使用することができる。 It does not specifically limit as a collector used for manufacture of the positive electrode of this embodiment, The normal collector which can be used for lithium ion batteries, such as aluminum foil, can be used.
本実施形態のリチウムイオン電池用正極は、必要に応じてプレスをおこない、正極の密度を調整してもよい。プレスの方法としては、一般的に公知の方法を用いることができる。 The positive electrode for a lithium ion battery of the present embodiment may be pressed if necessary to adjust the density of the positive electrode. As a method of pressing, generally known methods can be used.
［リチウムイオン電池］
つぎに、本実施形態に係るリチウムイオン電池１００について説明する。図１は、本発明に係る実施形態のリチウムイオン電池の構造の一例を示す断面図である。
[Lithium ion battery]
Below, the
本実施形態に係る全固体型リチウムイオン電池１００は、例えば、正極１１０と、電解質層１２０と、負極１３０とを備えている。そして、正極１１０が、本実施形態に係るリチウムイオン電池用正極１００である。
本実施形態のリチウムイオン電池１００は、一般的に公知の方法に準じて製造される。例えば、本実施形態の正極および負極をセパレーター中心に重ねたものを、円筒型、コイン型、角型、フィルム型その他任意の形状に形成し非水電解液を封入することにより作製される。
The all-solid-state
The
（非水電解液）
本実施形態の非水電解液とは、電解質を溶媒に溶解させたものである。
(Non-aqueous electrolyte)
The non-aqueous electrolytic solution of the present embodiment is one in which an electrolyte is dissolved in a solvent.
（電解質）
上記電解質としては、公知のリチウム塩がいずれも使用でき、活物質の種類に応じて選択すればよい。例えば、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＣＦ３ＳＯ３、ＬｉＣＦ３ＣＯ２、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＢ１０Ｃｌ１０、ＬｉＡｌＣｌ４、ＬｉＣｌ、ＬｉＢｒ、ＬｉＢ（Ｃ２Ｈ５）４、ＣＦ３ＳＯ３Ｌｉ、ＣＨ３
ＳＯ３Ｌｉ、ＬｉＣＦ３ＳＯ３、ＬｉＣ４Ｆ９ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、低級脂肪酸カルボン酸リチウムなどが挙げられる。
(Electrolytes)
Any known lithium salt can be used as the electrolyte, and it may be selected according to the type of active material. For example, LiClO 4, LiBF 4, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiB 10 Cl 10, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) 4, CF 3 SO 3 Li, CH 3
SO 3 Li, LiCF 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N, lithium lower fatty acid carboxylate and the like can be mentioned.
上記電解質を溶解する溶媒としては、電解質を溶解させる液体として通常用いられるものであれば特に限定されず、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、メチルエチルカーボネート（ＭＥＣ）、ビニレンカーボネート（ＶＣ）などのカーボネート類；γ−ブチロラクトン、γ−バレロラクトンなどのラクトン類；トリメトキシメタン、１，２−ジメトキシエタン、ジエチルエーテル、２−エトキシエタン、テトラヒドロフラン、２−メチルテトラヒドロフランなどのエーテル類；ジメチルスルホキシドなどのスルホキシド類；１，３−ジオキソラン、４−メチル−１，３−ジオキソランなどのオキソラン類；アセトニトリル、ニトロメタン、ホルムアミド、ジメチルホルムアミドなどの含窒素類；ギ酸メチル、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチルなどの有機酸エステル類；リン酸トリエステルやジグライム類；トリグライム類；スルホラン、メチルスルホランなどのスルホラン類；３−メチル−２−オキサゾリジノンなどのオキサゾリジノン類；１，３−プロパンスルトン、１，４−ブタンスルトン、ナフタスルトンなどのスルトン類；などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 The solvent for dissolving the electrolyte is not particularly limited as long as it is generally used as a liquid for dissolving the electrolyte, and ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC) Carbonates such as diethyl carbonate (DEC), methyl ethyl carbonate (MEC), vinylene carbonate (VC); lactones such as γ-butyrolactone and γ-valerolactone; trimethoxymethane, 1,2-dimethoxyethane, diethyl ether , Ethers such as 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran; sulfoxides such as dimethyl sulfoxide; oxolanes such as 1,3-dioxolane, 4-methyl-1,3-dioxolane; Nitrogen-containing compounds such as acetonitrile, nitromethane, formamide and dimethylformamide; organic acid esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate and ethyl propionate; phosphoric acid triesters and diglymes; triglymes Sulfolanes such as sulfolane and methyl sulfolane; oxazolidinones such as 3-methyl-2-oxazolidinone; and sultones such as 1,3-propane sultone, 1,4-butane sultone and naphtha sultone. These may be used singly or in combination of two or more.
本実施形態のセパレーターとしては正極と負極を電気的に絶縁させ、リチウムイオンを透過する機能を有するものであれば特に限定されないが、例えば、多孔性膜を用いることができる。 The separator of the present embodiment is not particularly limited as long as it has a function of electrically insulating the positive electrode and the negative electrode and transmitting lithium ions, but for example, a porous film can be used.
多孔性膜としては微多孔性高分子フィルムが好適に使用され、材質としてポリオレフィン、ポリイミド、ポリフッ化ビニリデン、ポリエステルなどが挙げられる。特に、多孔性ポリオレフィンフィルムが好ましく、具体的には多孔性ポリエチレンフィルム、多孔性ポリプロピレンフィルムなどが挙げられる。 As the porous membrane, a microporous polymer film is suitably used, and as the material, polyolefin, polyimide, polyvinylidene fluoride, polyester and the like can be mentioned. In particular, a porous polyolefin film is preferable, and specifically, a porous polyethylene film, a porous polypropylene film and the like can be mentioned.
（負極）
本実施形態のリチウムイオン電池用負極は特に限定されず、リチウムイオン電池に一般的に用いられているものを使用することができる。本実施形態の負極は特に限定されないが、一般的に公知の方法に準じて製造することができる。例えば、負極活物質を含む負極活物質層を銅などの集電体の表面に形成することにより得られる。
(Negative electrode)
The negative electrode for a lithium ion battery of the present embodiment is not particularly limited, and those generally used for lithium ion batteries can be used. The negative electrode of the present embodiment is not particularly limited, but can be manufactured according to a generally known method. For example, it can be obtained by forming a negative electrode active material layer containing a negative electrode active material on the surface of a current collector such as copper.
本実施形態の負極活物質としては、リチウムイオン電池の負極に使用可能な通常の負極活物質であれば特に限定されないが、例えば、天然黒鉛、人造黒鉛、樹脂炭、炭素繊維、活性炭、ハードカーボン、ソフトカーボンなどの炭素材料；リチウム金属、リチウム合金などのリチウム系金属；シリコン、スズなどの金属；ポリアセン、ポリアセチレン、ポリピロールなどの導電性ポリマーなどが挙げられる。 The negative electrode active material of the present embodiment is not particularly limited as long as it is a common negative electrode active material that can be used for the negative electrode of a lithium ion battery, for example, natural graphite, artificial graphite, resin charcoal, carbon fiber, activated carbon, hard carbon And carbon materials such as soft carbon; lithium metals such as lithium metal and lithium alloy; metals such as silicon and tin; and conductive polymers such as polyacene, polyacetylene and polypyrrole.
（全固体リチウムイオン電池）
本実施形態のリチウムイオン電池は電解質として、上述した非水電解液の代わりに、固体電解質を用いることによって全固体リチウムイオン電池とすることができる。
本実施形態の全固体リチウムイオン電池は、例えば、本実施形態の正極、負極、および、上記正極と上記負極との間に固体電解質により形成された固体電解質層を有するものである。
本実施形態の固体電解質としては特に限定されないが、一般的に公知のものを用いることができる。例えば、上述した正極に含ませる固体電解質と同様のものを用いることができる。
全固体リチウムイオン電池の正極活物質として、本実施形態の正極活物質を用いると、充放電効率、サイクル特性などの電池特性が良好で、かつ、高い安全性を有するリチウムイオン電池とすることができる。
(All solid lithium ion battery)
The lithium ion battery of this embodiment can be made into an all solid lithium ion battery by using a solid electrolyte as an electrolyte instead of the non-aqueous electrolyte described above.
The all solid lithium ion battery of the present embodiment has, for example, the positive electrode of the present embodiment, a negative electrode, and a solid electrolyte layer formed of a solid electrolyte between the positive electrode and the negative electrode.
The solid electrolyte of the present embodiment is not particularly limited, but generally known ones can be used. For example, the same solid electrolyte as that contained in the positive electrode described above can be used.
When the positive electrode active material of the present embodiment is used as a positive electrode active material of an all solid lithium ion battery, a lithium ion battery having good battery characteristics such as charge / discharge efficiency and cycle characteristics and high safety may be provided. it can.
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。
なお、本発明は前述の実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良などは本発明に含まれるものである。
以下、参考形態の例を付記する。
＜付記＞
（付記１）
構成元素として、Ｌｉ、Ｍｏ、およびＳを含む、リチウムイオン電池用正極活物質。
（付記２）
付記１に記載のリチウムイオン電池用正極活物質において、
前記Ｍｏの含有量に対する前記Ｌｉの含有量のモル比（Ｌｉ／Ｍｏ）が２以上２０以下であり、前記Ｍｏの含有量に対する前記Ｓの含有量のモル比（Ｓ／Ｍｏ）が、３以上１３以下である、リチウムイオン電池用正極活物質。
（付記３）
付記１または２に記載のリチウムイオン電池用正極活物質において、
レーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径ｄ ５０ が０．５μｍ以上２０μｍ以下である、リチウムイオン電池用正極活物質。
（付記４）
付記１乃至３いずれか一つに記載のリチウムイオン電池用正極活物質において、
原料であるＭｏＳ ２ 、およびＬｉ ２ Ｓを粉砕混合することにより得られる、リチウムイオン電池用正極活物質。
（付記５）
付記１乃至３いずれか一つに記載のリチウムイオン電池用正極活物質において、
原料であるＭｏＳ ２ 、Ｌｉ ２ Ｓ、およびＳを粉砕混合することにより得られる、リチウムイオン電池用正極活物質。
（付記６）
付記４または５に記載のリチウムイオン電池用正極活物質において、
前記Ｌｉ ２ Ｓに対する前記ＭｏＳ ２ の反応モル比（ＭｏＳ ２ ／Ｌｉ ２ Ｓ）が０．０５以上１．２以下である、リチウムイオン電池用正極活物質。
（付記７）
付記１乃至６いずれか一つに記載のリチウムイオン電池用正極活物質を主成分として含む、リチウムイオン電池用正極材料。
（付記８）
付記７に記載のリチウムイオン電池用正極材料において、
導電助剤をさらに含む、リチウムイオン電池用正極材料。
（付記９）
付記７または８に記載のリチウムイオン電池用正極材料において、
固体電解質をさらに含む、リチウムイオン電池用正極材料。
（付記１０）
付記７乃至９いずれか一つに記載のリチウムイオン電池用正極材料からなる正極活物質層を集電体の表面に形成してなる、リチウムイオン電池用正極。
（付記１１）
付記１０に記載のリチウムイオン電池用正極と、電解質層と、負極とを備えた、リチウムイオン電池。
（付記１２）
付記１１に記載のリチウムイオン電池において、
前記電解質層が固体電解質により形成されたものである、リチウムイオン電池。
As mentioned above, although embodiment of this invention was described, these are the illustrations of this invention, and various structures other than the above can also be employ | adopted.
Note that the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like in the range in which the object of the present invention can be achieved are included in the present invention.
Hereinafter, an example of a reference form is added.
<Supplementary Note>
(Supplementary Note 1)
The positive electrode active material for lithium ion batteries which contains Li, Mo, and S as a constitutent element.
(Supplementary Note 2)
In the positive electrode active material for a lithium ion battery according to supplementary note 1,
The molar ratio (Li / Mo) of the content of Li to the content of Mo is 2 or more and 20 or less, and the molar ratio (S / Mo) of the content of S to the content of Mo is 3 or more The positive electrode active material for lithium ion batteries which is 13 or less.
(Supplementary Note 3)
In the positive electrode active material for a lithium ion battery according to supplementary note 1 or 2,
The average particle size d 50 is 0.5μm or more 20μm or less, the positive electrode active material for lithium ion batteries in weight particle size distribution by a laser diffraction scattering particle size distribution measuring method.
(Supplementary Note 4)
The positive electrode active material for a lithium ion battery according to any one of supplementary notes 1 to 3,
MoS 2 as a raw material, and obtained by the Li 2 S pulverized and mixed, the positive electrode active material for lithium ion batteries.
(Supplementary Note 5)
The positive electrode active material for a lithium ion battery according to any one of supplementary notes 1 to 3,
Raw material is MoS 2, Li 2 S, and obtained by the S pulverized and mixed, the positive electrode active material for lithium ion batteries.
(Supplementary Note 6)
In the positive electrode active material for a lithium ion battery according to supplementary note 4 or 5,
The Li 2 reaction molar ratio of the MoS 2 for S (MoS 2 / Li 2 S) is 0.05 to 1.2, the positive electrode active material for lithium ion batteries.
(Appendix 7)
The positive electrode material for lithium ion batteries which contains the positive electrode active material for lithium ion batteries as described in any one of Additional remark 1 thru | or 6 as a main component.
(Supplementary Note 8)
In the positive electrode material for a lithium ion battery according to supplementary note 7,
The positive electrode material for lithium ion batteries which further contains a conductive support agent.
(Appendix 9)
In the positive electrode material for a lithium ion battery according to supplementary note 7 or 8,
A positive electrode material for a lithium ion battery, further comprising a solid electrolyte.
(Supplementary Note 10)
The positive electrode for a lithium ion battery formed by forming the positive electrode active material layer comprising the positive electrode material for a lithium ion battery according to any one of appendices 7 to 9 on the surface of a current collector.
(Supplementary Note 11)
A lithium ion battery comprising the positive electrode for a lithium ion battery according to appendix 10, an electrolyte layer, and a negative electrode.
(Supplementary Note 12)
In the lithium ion battery described in appendix 11,
The lithium ion battery whose said electrolyte layer is formed of a solid electrolyte.
以下、本発明を実施例および比較例により説明するが、本発明はこれらに限定されるものではない。なお、実施例、比較例では、「ｍＡｈ／ｇ」は正極活物質１ｇあたりの容量密度を示す。 Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “mAh / g” indicates the capacity density per 1 g of the positive electrode active material.
［１］測定方法
はじめに、以下の実施例、比較例における測定方法を説明する。
[1] Measurement Method First, measurement methods in the following Examples and Comparative Examples will be described.
（１）粒度分布
レーザー回折散乱式粒度分布測定装置（マルバーン社製、マスターサイザー３０００）を用いて、レーザー回折法により、実施例および比較例で得られた正極活物質の粒度分布を測定した。測定結果から、各正極活物質について、重量基準の累積分布における５０％累積時の粒径（ｄ５０、平均粒子径）をそれぞれ求めた。また、同様にして、各原料の平均粒子径をそれぞれ求めた。
(1) Particle Size Distribution The particle size distribution of the positive electrode active material obtained in Examples and Comparative Examples was measured by a laser diffraction method using a laser diffraction scattering type particle size distribution measuring apparatus (Mastersizer 3000 manufactured by Malvern Co., Ltd.). From the measurement results, for each positive electrode active material, the particle size (d 50 , average particle size) at 50% accumulation in the cumulative distribution on a weight basis was determined. Further, in the same manner, the average particle diameter of each raw material was determined.
（２）ＩＣＰ発光分光分析
ＩＣＰ発光分光分析装置（セイコーインスツルメント社製、ＳＰＳ３０００）を用いて、ＩＣＰ発光分光分析法により測定し、実施例および比較例で得られた正極活物質中の各元素の質量％をそれぞれ求め、それらの値に基づいて、各元素のモル比をそれぞれ計算した。
(2) ICP emission spectrometry using ICP emission spectrometry (manufactured by Seiko Instruments Inc., SPS 3000) by ICP emission spectrometry, each of the positive electrode active materials obtained in Examples and Comparative Examples The mass% of each element was determined, and the molar ratio of each element was calculated based on those values.
（３）充放電試験
アルゴン雰囲気下で、実施例および比較例で得られた正極活物質を３３３ｍｇと、導電助剤であるアセチレンブラックを３３３ｍｇと、固体電解質であるＬｉ１０Ｐ３Ｓ１２を３３３ｍｇとをＡｌ２Ｏ３製ポットに入れ、ＺｒＯ２ボールを加えてＡｌ２Ｏ３製ポットを密閉した。次いで、Ａｌ２Ｏ３製ポットをボールミル回転台に乗せ、９７ｒｐｍで、２４時間混合した。混合後の粉末はプレス成型を行い、正極活物質層を得た（直径φ＝１４ｍｍ、厚みｔ＝０．０３ｍｍ、３．２ｍｇ）。次いで、その正極活物質層を集電体であるアルミ箔に導電性アクリル粘着層を介して圧着させ、正極を作製した。導電性アクリル粘着層の導電材にはＮｉ微粒子を使用した。
また、上記方法で得られた正極、固体電解質層（Ｌｉ１０Ｐ３Ｓ１２、１００ｍｇ）、負極であるインジウム箔（φ＝１４ｍｍ、ｔ＝０．５ｍｍ）をこの順で積層させて全固体リチウムイオン電池を作製した。次いで、得られた全固体リチウムイオン電池について、電流密度６５μＡ／ｃｍ２の条件で充電終止電位３．０Ｖまで充電した後、電流密度６５μＡ／ｃｍ２の条件で、放電終止電位０．４Ｖまで放電させる条件で充放電を１０回行った。
ここで、１回目の放電容量を１００％としたときの１０回目の放電容量を放電容量変化率［％］とした。
(3) Charge / Discharge Test Under an argon atmosphere, 333 mg of the positive electrode active material obtained in Examples and Comparative Examples, 333 mg of acetylene black as a conductive additive, and 333 mg of Li 10 P 3 S 12 as a solid electrolyte Was placed in an Al 2 O 3 pot, a ZrO 2 ball was added, and the Al 2 O 3 pot was sealed. Next, the Al 2 O 3 pot was placed on a ball mill rotary table and mixed at 97 rpm for 24 hours. The powder after mixing was press-molded to obtain a positive electrode active material layer (diameter φ = 14 mm, thickness t = 0.03 mm, 3.2 mg). Then, the positive electrode active material layer was pressure-bonded to an aluminum foil as a current collector via a conductive acrylic pressure-sensitive adhesive layer to prepare a positive electrode. Ni fine particles were used as the conductive material of the conductive acrylic adhesive layer.
In addition, the positive electrode obtained by the above method, the solid electrolyte layer (Li 10 P 3 S 12 , 100 mg), and the indium foil (φ = 14 mm, t = 0.5 mm) as the negative electrode are laminated in this order to obtain all solid lithium. An ion battery was produced. Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.0V at a current density of 65μA / cm 2, at a current density of 65μA / cm 2, until the discharge cutoff potential 0.4V discharge Charge and discharge were performed 10 times under the conditions of
Here, the discharge capacity change rate [%] is defined as the tenth discharge capacity when the first discharge capacity is 100%.
［２］正極活物質の製造
＜実施例１＞
アルゴン雰囲気下で、Ａｌ２Ｏ３製ポットに、ＭｏＳ２（和光純薬工業社製、９７０ｍｇ、６．１ｍｍｏｌ、平均粒子径：１０μｍ）と、Ｌｉ２Ｓ（シグマアルドリッチジャパン社製、８３５ｍｇ、１８．２ｍｍｏｌ、平均粒子径：５μｍ）と、Ｓ（シグマアルドリッチジャパン社製、１９４ｍｇ、６．１ｍｍｏｌ）とを秤量して加え、さらにＺｒＯ２ボールを入れ、Ａｌ２Ｏ３製ポットを密閉した。
次いで、Ａｌ２Ｏ３製ポットを、ボールミル回転台に乗せ９７ｒｐｍで、４日間処理を行い、混合物を得た。
[2] Production of Positive Electrode Active Material <Example 1>
Mo S 2 (manufactured by Wako Pure Chemical Industries, 970 mg, 6.1 mmol, average particle size: 10 μm) and Li 2 S (manufactured by Sigma Aldrich Japan, 835 mg, 18) in an Al 2 O 3 pot under an argon atmosphere .2 mmol, average particle diameter: 5 μm, and S (manufactured by Sigma Aldrich Japan, 194 mg, 6.1 mmol) were weighed and added, further ZrO 2 balls were added, and the Al 2 O 3 pot was sealed.
Next, the Al 2 O 3 pot was placed on a ball mill rotary table and treated at 97 rpm for 4 days to obtain a mixture.
得られた正極活物質は乳鉢により粉砕し、目開き４３μｍの篩により分級して、平均粒子径ｄ５０が５μｍの正極活物質１を得た。 The obtained positive electrode active material was pulverized by a mortar and classified by a sieve with 43 μm openings to obtain a positive electrode active material 1 having an average particle diameter d 50 of 5 μm.
＜実施例２＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を１７４２ｍｇ（１０．９ｍｍｏｌ）、Ｌｉ２Ｓの投入量を５００ｍｇ（１０．９ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が１０μｍの正極活物質２を得た。
Example 2
Example 1 except that 1742 mg (10.9 mmol) of MoS 2 was added to the Al 2 O 3 pot, 500 mg (10.9 mmol) of Li 2 S was changed to 0 mg, and the amount of S was changed to 0 mg. In the same manner as in the above, a positive electrode active material 2 having an average particle diameter d 50 of 10 μm was obtained.
＜実施例３＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を１４２４ｍｇ（８．９ｍｍｏｌ）、Ｌｉ２Ｓの投入量を８１８ｍｇ（１７．８ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が７μｍの正極活物質３を得た。
Example 3
Example 1 except that 1424 mg (8.9 mmol) of MoS 2 was introduced into the Al 2 O 3 pot, 818 mg (17.8 mmol) of Li 2 S was introduced, and 0 mg of S was introduced. In the same manner as in the above, a positive electrode active material 3 having an average particle diameter d 50 of 7 μm was obtained.
＜実施例４＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を１２０５ｍｇ（７．５ｍｍｏｌ）、Ｌｉ２Ｓの投入量を１０３７ｍｇ（２２．６ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が５μｍの正極活物質４を得た。
Example 4
Example 1 except that the amount of MoS 2 to be introduced into the Al 2 O 3 pot was changed to 1205 mg (7.5 mmol), the amount of Li 2 S to 1037 mg (22.6 mmol), and the amount of S to 0 mg. In the same manner as in the above, a positive electrode active material 4 having an average particle diameter d 50 of 5 μm was obtained.
＜実施例５＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を１０４４ｍｇ（６．５ｍｍｏｌ）、Ｌｉ２Ｓの投入量を１１９８ｍｇ（２６．０８ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が４μｍの正極活物質５を得た。
Example 5
Example 1 except that 1044 mg (6.5 mmol) of MoS 2 was introduced into the Al 2 O 3 pot, 1198 mg (26.08 mmol) of Li 2 S was introduced, and 0 mg of S was introduced. In the same manner as in the above, a positive electrode active material 5 having an average particle diameter d 50 of 4 μm was obtained.
＜実施例６＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を９２１ｍｇ（５．８ｍｍｏｌ）、Ｌｉ２Ｓの投入量を１３２１ｍｇ（２８．８ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が４μｍの正極活物質６を得た。
Example 6
Example 1 except that 921 mg (5.8 mmol) of MoS 2 was added to the Al 2 O 3 pot, 1321 mg (28.8 mmol) of Li 2 S was added, and 0 mg of S was added. In the same manner as in the above, a positive electrode active material 6 having an average particle diameter d 50 of 4 μm was obtained.
＜実施例７＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を８２４ｍｇ（５．１ｍｍｏｌ）、Ｌｉ２Ｓの投入量を１４１８ｍｇ（３０．９ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が３μｍの正極活物質７を得た。
Example 7
Example 1 except that 824 mg (5.1 mmol) of MoS 2 was introduced into the Al 2 O 3 pot, 1418 mg (30.9 mmol) of Li 2 S was introduced, and 0 mg of S was introduced. In the same manner as in the above, a positive electrode active material 7 having an average particle diameter d 50 of 3 μm was obtained.
＜実施例８＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を７４５ｍｇ（４．７ｍｍｏｌ）、Ｌｉ２Ｓの投入量を１４９７ｍｇ（３２．５ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が２μｍの正極活物質８を得た。
Example 8
Example 1 except that 745 mg (4.7 mmol) of MoS 2 was introduced into the Al 2 O 3 pot, 1497 mg (32.5 mmol) of Li 2 S was introduced, and 0 mg of S was introduced. In the same manner as in the above, a positive electrode active material 8 having an average particle diameter d 50 of 2 μm was obtained.
＜実施例９＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を６８０ｍｇ（４．２ｍｍｏｌ）、Ｌｉ２Ｓの投入量を１５６２ｍｇ（３４．０ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が２μｍの正極活物質９を得た。
Example 9
Example 1 except that the amount of MoS 2 to be added to the Al 2 O 3 pot was changed to 680 mg (4.2 mmol), the amount of Li 2 S to 1562 mg (34.0 mmol), and the amount of S to 0 mg. In the same manner as in the above, a positive electrode active material 9 having an average particle diameter d 50 of 2 μm was obtained.
＜実施例１０＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を６２６ｍｇ（３．９ｍｍｏｌ）、Ｌｉ２Ｓの投入量を１６１６ｍｇ（３５．２ｍｍｏｌ）、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が１μｍの正極活物質１０を得た。
Example 10
Example 1 except that the amount of MoS 2 charged into the Al 2 O 3 pot was changed to 626 mg (3.9 mmol), the amount of Li 2 S charged to 1616 mg (35.2 mmol), and the amount of S charged to 0 mg. In the same manner as in the above, a positive electrode active material 10 having an average particle diameter d 50 of 1 μm was obtained.
＜実施例１１＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を１３４４ｍｇ（８．４ｍｍｏｌ）、Ｌｉ２Ｓの投入量を３８６ｍｇ（８．４ｍｍｏｌ）、Ｓの投入量を２６９ｍｇ（９．０ｍｍｏｌ）に変えた以外は実施例１と同様にして、平均粒子径ｄ５０が１２μｍの正極活物質１１を得た。
Example 11
The amount of MoS 2 to be added to the Al 2 O 3 pot was changed to 1344 mg (8.4 mmol), the amount of Li 2 S to 386 mg (8.4 mmol), and the amount of S to 269 mg (9.0 mmol) otherwise in the same manner as in example 1, the average particle size d 50 to obtain a positive electrode active material 11 of the 12 [mu] m.
＜実施例１２＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を１１２７ｍｇ（７．０ｍｍｏｌ）、Ｌｉ２Ｓの投入量を６４７ｍｇ（１４．１ｍｍｏｌ）、Ｓの投入量を２２６ｍｇ（７．０ｍｍｏｌ）に変えた以外は実施例１と同様にして、平均粒子径ｄ５０が１０μｍの正極活物質１２を得た。
Example 12
1127 mg (7.0 mmol) of MoS 2 was added to the Al 2 O 3 pot, 647 mg (14.1 mmol) of Li 2 S was changed to 226 mg (7.0 mmol) of S. A positive electrode active material 12 having an average particle diameter d 50 of 10 μm was obtained in the same manner as in Example 1 except for the above.
＜実施例１３＞
Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を６８４ｍｇ（４．３ｍｍｏｌ）、Ｌｉ２Ｓの投入量を１１７８ｍｇ（２５．６ｍｍｏｌ）、Ｓの投入量を１３７ｍｇ（４．３ｍｍｏｌ）に変えた以外は実施例１と同様にして、平均粒子径ｄ５０が５μｍの正極活物質１３を得た。
Example 13
The amount of MoS 2 to be added to the Al 2 O 3 pot was 684 mg (4.3 mmol), the amount of Li 2 S was changed to 1178 mg (25.6 mmol), and the amount of S was changed to 137 mg (4.3 mmol) otherwise in the same manner as in example 1, the average particle size d 50 to obtain a positive electrode active material 13 of 5 [mu] m.
＜比較例１＞Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を１９９９ｍｇ（１２．４ｍｍｏｌ）、Ｌｉ２Ｓの投入量を０ｍｇ、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が８μｍの正極活物質１４を得た。 <Comparative Example 1> Example 1 except that the input amount of MoS 2 to be introduced into the Al 2 O 3 pot was changed to 1999 mg (12.4 mmol), the input amount of Li 2 S was changed to 0 mg, and the input amount of S was changed to 0 mg. In the same manner as in the above, a positive electrode active material 14 having an average particle diameter d 50 of 8 μm was obtained.
＜比較例２＞Ａｌ２Ｏ３製ポットに投入するＭｏＳ２の投入量を１６６５ｍｇ（８．７ｍｍｏｌ）、Ｌｉ２Ｓの投入量を０ｍｇ、Ｓの投入量を３３４ｍｇ（１０．４ｍｍｏｌ）に変えた以外は実施例１と同様にして、平均粒子径ｄ５０が１２μｍの正極活物質１５を得た。 <Comparative Example 2> The amount of MoS 2 to be introduced into the Al 2 O 3 pot was changed to 1665 mg (8.7 mmol), the amount of Li 2 S to 0 mg, and the amount of S to 334 mg (10.4 mmol). otherwise in the same manner as in example 1, the average particle size d 50 to obtain a positive electrode active material 15 of the 12 [mu] m.
＜比較例３＞Ａｌ２Ｏ３製ポットに投入するＬｉ２Ｓの投入量を１９９９ｍｇ（４３．５ｍｍｏｌ）、ＭｏＳ２の投入量を０ｍｇ、Ｓの投入量を０ｍｇに変えた以外は実施例１と同様にして、平均粒子径ｄ５０が１μｍの正極活物質１６を得た。 Comparative Example 3 Example 1 except that 1999 mg (43.5 mmol) of Li 2 S was charged into the Al 2 O 3 pot, 0 mg of MoS 2 was charged, and 0 mg of S was changed to 0 mg. In the same manner as in the above, a positive electrode active material 16 having an average particle diameter d 50 of 1 μm was obtained.
以上の正極活物質１〜１６のＬｉ／Ｍｏのモル比、Ｓ／Ｍｏのモル比および充放電試験結果を表１に示す。
実施例で得られた正極活物質１〜１３は、比較例で得られた正極活物質１４〜１６に比べて、サイクル特性が優れていた。
The molar ratio of Li / Mo, the molar ratio of S / Mo, and the charge / discharge test results of the positive electrode active materials 1 to 16 described above are shown in Table 1.
The positive electrode active materials 1 to 13 obtained in the examples were superior in cycle characteristics to the positive electrode active materials 14 to 16 obtained in the comparative example.
１００ リチウムイオン電池
１１０ 正極
１２０ 電解質層
１３０ 負極
100
Claims (12)
前記Ｌｉ−Ｍｏ−Ｓ化合物は、非晶質で、かつ、微粒子状であり、
前記Ｌｉ−Ｍｏ−Ｓ化合物中の前記Ｍｏの含有量に対する前記Ｌｉの含有量のモル比（Ｌｉ／Ｍｏ）が２以上２０以下であり、前記Ｍｏの含有量に対する前記Ｓの含有量のモル比（Ｓ／Ｍｏ）が３以上１３以下であり、
レーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径ｄ５０が０．５μｍ以上２０μｍ以下であり、
前記Ｌｉ−Ｍｏ−Ｓ化合物は、ＭｏＳ ２ およびＬｉ ２ Ｓのメカノケミカル処理物である、リチウムイオン電池用正極活物質。 As a constituent element, it contains only Li, Mo, and S, and contains a Li-Mo-S compound capable of absorbing and releasing lithium ions by charge and discharge,
The Li-Mo-S compound is amorphous and particulate.
The molar ratio (Li / Mo) of the content of Li to the content of Mo in the Li-Mo-S compound is 2 or more and 20 or less, and the molar ratio of the content of S to the content of Mo (S / Mo) is 3 or more and 13 or less,
Ri average particle diameter d 50 of Der least 20μm or less 0.5μm in weight particle size distribution by a laser diffraction scattering particle size distribution measuring method,
The Li-MoS compounds are mechanochemical treatment of MoS 2 and Li 2 S, positive electrode active material for lithium ion batteries.
前記Ｌｉ−Ｍｏ−Ｓ化合物は、非晶質で、かつ、微粒子状であり、
前記Ｌｉ−Ｍｏ−Ｓ化合物中の前記Ｍｏの含有量に対する前記Ｌｉの含有量のモル比（Ｌｉ／Ｍｏ）が２以上２０以下であり、前記Ｍｏの含有量に対する前記Ｓの含有量のモル比（Ｓ／Ｍｏ）が３以上１３以下であり、
レーザー回折散乱式粒度分布測定法による重量基準粒度分布における平均粒子径ｄ５０が０．５μｍ以上２０μｍ以下であり、
前記Ｌｉ−Ｍｏ−Ｓ化合物は、ＭｏＳ ２ 、Ｌｉ ２ Ｓ、およびＳのメカノケミカル処理物である、リチウムイオン電池用正極活物質。 As a constituent element, it contains only Li, Mo, and S, and contains a Li-Mo-S compound capable of absorbing and releasing lithium ions by charge and discharge,
The Li-Mo-S compound is amorphous and particulate.
The molar ratio (Li / Mo) of the content of Li to the content of Mo in the Li-Mo-S compound is 2 or more and 20 or less, and the molar ratio of the content of S to the content of Mo (S / Mo) is 3 or more and 13 or less,
Ri average particle diameter d 50 of Der least 20μm or less 0.5μm in weight particle size distribution by a laser diffraction scattering particle size distribution measuring method,
The Li-MoS compounds are mechanochemical treatment of MoS 2, Li 2 S, and S, the positive electrode active material for lithium ion batteries.
前記Ｌｉ２Ｓに対する前記ＭｏＳ２の混合モル比（ＭｏＳ２／Ｌｉ２Ｓ）が０．０５以上１．２以下である、リチウムイオン電池用正極活物質。 In the positive electrode active material for a lithium ion battery according to claim 1 or 2 ,
The Li 2 mixing molar ratio of the MoS 2 for S (MoS 2 / Li 2 S) is 0.05 to 1.2, the positive electrode active material for lithium ion batteries.
以下の方法により測定される、前記リチウムイオン電池用正極活物質の放電容量が１８６ｍＡｈ／ｇ以上である、リチウムイオン電池用正極活物質。
（方法）
アルゴン雰囲気下で、前記リチウムイオン電池用正極活物質を３３３ｍｇと、導電助剤であるアセチレンブラックを３３３ｍｇと、固体電解質であるＬｉ１０Ｐ３Ｓ１２を３３３ｍｇとをＡｌ２Ｏ３製ポットに入れ、ＺｒＯ２ボールを加えて前記Ａｌ２Ｏ３製ポットを密閉する。次いで、前記Ａｌ２Ｏ３製ポットをボールミル回転台に乗せ、９７ｒｐｍで、２４時間混合する。混合後の粉末に対してプレス成型を行い、正極活物質層を得る（直径φ＝１４ｍｍ、厚みｔ＝０．０３ｍｍ、３．２ｍｇ）。次いで前記正極活物質層を集電体であるアルミ箔に、導電材としてＮｉ微粒子を含む導電性アクリル粘着層を介して圧着させ、正極を作製する。次いで、前記正極、固体電解質層（Ｌｉ１０Ｐ３Ｓ１２、１００ｍｇ）、負極であるインジウム箔（φ＝１４ｍｍ、ｔ＝０．５ｍｍ）をこの順で積層させて全固体リチウムイオン電池を作製する。次いで、得られた全固体リチウムイオン電池について、電流密度６５μＡ／ｃｍ２の条件で充電終止電位３．０Ｖまで充電した後、電流密度６５μＡ／ｃｍ２の条件で、放電終止電位０．４Ｖまで放電させる条件で充放電をおこない、放電容量を測定し、得られた放電容量を前記リチウムイオン電池用正極活物質の放電容量とする。 The positive electrode active material for a lithium ion battery according to any one of claims 1 to 3 .
The positive electrode active material for lithium ion batteries whose discharge capacity of the said positive electrode active material for lithium ion batteries measured by the following method is 186 mAh / g or more.
(Method)
Under an argon atmosphere, 333 mg of the positive electrode active material for a lithium ion battery, 333 mg of acetylene black as a conduction aid, 333 mg of Li 10 P 3 S 12 as a solid electrolyte are put in an Al 2 O 3 pot Add a ZrO 2 ball and seal the Al 2 O 3 pot. Then, the Al 2 O 3 pot is placed on a ball mill rotary table and mixed at 97 rpm for 24 hours. The powder after mixing is subjected to press molding to obtain a positive electrode active material layer (diameter φ = 14 mm, thickness t = 0.03 mm, 3.2 mg). Then, the positive electrode active material layer is pressure-bonded to an aluminum foil as a current collector via a conductive acrylic pressure-sensitive adhesive layer containing Ni fine particles as a conductive material to produce a positive electrode. Then, the positive electrode, the solid electrolyte layer (Li 10 P 3 S 12 , 100 mg), and the indium foil (φ = 14 mm, t = 0.5 mm) which is a negative electrode are laminated in this order to prepare an all solid lithium ion battery. . Next, the all solid state lithium ion battery obtained was charged to a charge termination voltage 3.0V at a current density of 65μA / cm 2, at a current density of 65μA / cm 2, until the discharge cutoff potential 0.4V discharge The charge and discharge are performed under the conditions to be measured, the discharge capacity is measured, and the obtained discharge capacity is used as the discharge capacity of the positive electrode active material for a lithium ion battery.
導電助剤をさらに含む、リチウムイオン電池用正極材料。 In the positive electrode material for a lithium ion battery according to claim 5 ,
The positive electrode material for lithium ion batteries which further contains a conductive support agent.
固体電解質をさらに含む、リチウムイオン電池用正極材料。 In the positive electrode material for a lithium ion battery according to claim 5 or 6 ,
A positive electrode material for a lithium ion battery, further comprising a solid electrolyte.
前記電解質層が固体電解質により形成されたものである、リチウムイオン電池。 In the lithium ion battery according to claim 9 ,
The lithium ion battery whose said electrolyte layer is formed of a solid electrolyte.
ＭｏＳ２およびＬｉ２Ｓをメカノケミカル処理する工程を含むリチウムイオン電池用正極活物質の製造方法。 It is a manufacturing method for manufacturing the quality of cathode active material for lithium ion batteries according to claim 1 ,
The method for producing a positive electrode active material for a lithium ion battery comprising MoS 2 and Li 2 steps S to mechanochemical processing.
ＭｏＳ２、Ｌｉ２Ｓ、およびＳをメカノケミカル処理する工程を含むリチウムイオン電池用正極活物質の製造方法。 It is a manufacturing method for manufacturing the quality of cathode active material for lithium ion batteries according to claim 2 ,
MoS 2, Li 2 S, and method for producing a cathode active material for lithium ion batteries comprising the step of mechanochemical processing S.
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