JP2005327528A - Solid electrolyte-containing electrode for lithium secondary battery - Google Patents

Solid electrolyte-containing electrode for lithium secondary battery Download PDF

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JP2005327528A
JP2005327528A JP2004143209A JP2004143209A JP2005327528A JP 2005327528 A JP2005327528 A JP 2005327528A JP 2004143209 A JP2004143209 A JP 2004143209A JP 2004143209 A JP2004143209 A JP 2004143209A JP 2005327528 A JP2005327528 A JP 2005327528A
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solid electrolyte
active material
positive electrode
particles
secondary battery
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JP4800589B2 (en
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Shin Fujitani
伸 藤谷
Kumiko Kanai
久美子 金井
Masahisa Fujimoto
正久 藤本
Masahiro Tatsumisuna
昌弘 辰己砂
Akitoshi Hayashi
晃敏 林
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Osaka Prefecture
Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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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

Abstract

<P>PROBLEM TO BE SOLVED: To improve charge/discharge cycle characteristics in an electrode containing a solid electrolyte having lithium ion conductivity and used in a secondary battery. <P>SOLUTION: In the electrode containing the solid electrolyte having lithium ion conductivity and used in the lithium secondary battery, solid electrolyte particles having lithium ion conductivity formed by mechanical milling treatment are mixed with and dispersed in positive active material powder not practically containing particles having a particle size of 30 μm or more, preferably not practically containing particles having a particle size of 2 μm or less. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、リチウム二次電池に用いるリチウムイオン導電性の固体電解質を含有した電極に関するものである。   The present invention relates to an electrode containing a lithium ion conductive solid electrolyte used for a lithium secondary battery.

近年、携帯電話及び持ち運び可能な電子機器が広く普及している。従来より、これらの携帯用電子機器には各種の化学電池が使用されているが、安全性や信頼性の点で解決すべき問題は多い。漏液、安全性などにおける不安を解消するため、将来的には電池の全固体化を行うことが強く求められている。   In recent years, mobile phones and portable electronic devices have become widespread. Conventionally, various types of chemical batteries have been used in these portable electronic devices, but there are many problems to be solved in terms of safety and reliability. In order to eliminate concerns about leakage, safety, etc., there is a strong demand for solidification of the battery in the future.

このため、イオン導電性の固体電解質、特に蓄電性の高いリチウム二次電池を構成するとができるリチウムイオン導電性の固体電解質に関する検討が行われている（例えば、非特許文献１）。   For this reason, studies have been made on ion-conductive solid electrolytes, particularly lithium-ion conductive solid electrolytes that can constitute lithium secondary batteries with high power storage (for example, Non-Patent Document 1).

このような固体電解質の中でも、導電性の高いガラス固体電解質粒子をメカニカルミリング処理で合成し、これをＬｉＣｏＯ2などの正極活物質と混合して固体電解質を含有する電極を作製する試みがなされている（例えば、特許文献１）。 Among such solid electrolytes, attempts have been made to synthesize high-conductivity glass solid electrolyte particles by mechanical milling and mix them with a positive electrode active material such as LiCoO 2 to produce an electrode containing the solid electrolyte. (For example, Patent Document 1).

しかしながら、このようなガラス固体電解質粒子を用いた場合に、どのような電極構造のものが良好な特性を示すかについて詳細には検討されていない。
特開２００１−２７３９２８号公報 Electrochemistry 69, No. 10 (2001)p793-797 However, when such glass solid electrolyte particles are used, it has not been studied in detail what kind of electrode structure exhibits good characteristics.
JP 2001-293928 A Electrochemistry 69, No. 10 (2001) p793-797

本発明の目的は、リチウム二次電池に用いるリチウムイオン導電性の固体電解質を含有した電極であって、電気化学容量が高く、かつ充放電サイクル特性に優れた電極及びこれを用いたリチウム二次電池を提供することにある。   An object of the present invention is an electrode containing a lithium ion conductive solid electrolyte for use in a lithium secondary battery, having high electrochemical capacity and excellent charge / discharge cycle characteristics, and a lithium secondary using the same To provide a battery.

本発明は、リチウム二次電池に用いるリチウムイオン導電性の固体電解質を含有した電極であって、メカニカルミリング処理により合成したリチウムイオン導電性の固体電解質粒子を、粒子径３０μｍ以上の粒子を実質的に含まない正極活物質粉体に混合して分散させたことを特徴としている。   The present invention is an electrode containing a lithium ion conductive solid electrolyte for use in a lithium secondary battery, and substantially comprises lithium ion conductive solid electrolyte particles synthesized by mechanical milling treatment with particles having a particle diameter of 30 μm or more. It is characterized by being mixed and dispersed in a positive electrode active material powder not included in the above.

メカニカルミリング処理により合成したリチウムイオン導電性の固体電解質粒子は、２〜１０μｍ程度の粒子径を有しており、この固体電解質粒子に、本発明に従い粒子径３０μｍ以上の粒子を実質的に含まない正極活物質粉体を混合して分散させることにより、固体電解質粒子と正極活物質粉体とを均一に分散して混合することができ、これによって充放電サイクル特性を向上させることができる。   The lithium ion conductive solid electrolyte particles synthesized by mechanical milling have a particle size of about 2 to 10 μm, and the solid electrolyte particles do not substantially contain particles having a particle size of 30 μm or more according to the present invention. By mixing and dispersing the positive electrode active material powder, the solid electrolyte particles and the positive electrode active material powder can be uniformly dispersed and mixed, thereby improving the charge / discharge cycle characteristics.

本発明において、正極活物質粉体は、粒子径２μｍ以下の粒子を実質的に含まないことがさらに好ましい。粒子径２μｍ以下の粒子を実質的に含まないことにより、さらに正極活物質粉体を均一に混合させることができ、さらに充放電サイクル特性を向上させることができる。   In the present invention, it is further preferable that the positive electrode active material powder does not substantially contain particles having a particle diameter of 2 μm or less. By substantially not including particles having a particle diameter of 2 μm or less, the positive electrode active material powder can be further uniformly mixed, and charge / discharge cycle characteristics can be further improved.

本発明において粒子径３０μｍ以上の粒子あるいは粒子径２μｍ以下の粒子を実質的に含まないとは、これらの粒子が粒子全体において２％以下であることを意味している。本発明において、粒子分布は、例えば、レーザー回折式粒度分布測定装置により測定することができる。   In the present invention, “substantially free of particles having a particle diameter of 30 μm or more or particles having a particle diameter of 2 μm or less means that these particles are 2% or less in the entire particle. In the present invention, the particle distribution can be measured by, for example, a laser diffraction particle size distribution measuring apparatus.

本発明によれば、リチウムイオン導電性の固体電解質粒子と正極活物質粉末とを均一に分散して混合することができ、充放電の繰り返しに対して安定な固体電解質／正極活物質の界面構造を形成することができる。このため、活物質の可逆的な充放電容量を高めることができ、充放電サイクルによっても可逆的な電気化学容量を高く維持できるため、充放電サイクル特性を向上させることができる。   According to the present invention, lithium ion conductive solid electrolyte particles and positive electrode active material powder can be uniformly dispersed and mixed, and the solid electrolyte / positive electrode active material interface structure is stable against repeated charge and discharge. Can be formed. For this reason, since the reversible charging / discharging capacity | capacitance of an active material can be raised and a reversible electrochemical capacity | capacitance can be maintained high also by a charging / discharging cycle, charging / discharging cycling characteristics can be improved.

本発明において用いる固体電解質は、メカニカルミリング処理により合成されるリチウムイオン導電性の固体電解質であれば特に限定されるものではないが、ガラス固体電解質であることが好ましく、特にリチウムイオン導電性の高いＬｉ2Ｓ−ＳｉＳ2−Ｐ2Ｓ5が好ましく用いられる。 The solid electrolyte used in the present invention is not particularly limited as long as it is a lithium ion conductive solid electrolyte synthesized by mechanical milling treatment, but is preferably a glass solid electrolyte, and particularly high in lithium ion conductivity. Li 2 S—SiS 2 —P 2 S 5 is preferably used.

本発明において、正極活物質は、リチウムイオンを電気化学的に吸蔵・放出できるものであればよく、特に限定されるものではないが、電気化学容量が比較的大きく、金属リチウム基準で３Ｖ以上の電位をもつコバルトまたはニッケルの内の少なくとも１種類を含む層状岩塩型構造を有するリチウム含有遷移金属酸化物が好ましく用いられる。このような正極活物質として、例えば、ＬｉＣｏaＭ1-aＯ2（式中Ｍは、Ｂ、Ｍｇ、Ａｌ、Ｔｉ、Ｍｎ、Ｖ、Ｆｅ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、及びＩｎから選ばれる少なくとも１種類以上であり、ａは０＜ａ≦１を満足する。）で表わされるリチウムコバルト複合酸化物、及びＬｉＮｉbＭ1-bＯ2（式中Ｍは、Ｂ、Ｍｇ、Ａｌ、Ｔｉ、Ｍｎ、Ｖ、Ｆｅ、Ｃｏ、Ｃｕ、Ｚｎ、Ｇａ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、及びＩｎから選ばれる少なくとも１種類以上であり、ｂは０＜ｂ≦１を満足する。）で表わされるリチウムニッケル複合酸化物を挙げることができる。これらの中でも、ＬｉＣｏＯ2は電気化学容量が大きく、粉砕条件により粒度の調整が比較的容易であるため、本発明において特に好ましく用いられる。 In the present invention, the positive electrode active material is not particularly limited as long as it is capable of electrochemically occluding and releasing lithium ions. However, the positive electrode active material has a relatively large electrochemical capacity and is 3 V or more based on metallic lithium. A lithium-containing transition metal oxide having a layered rock salt structure containing at least one of potential cobalt or nickel is preferably used. As such a positive electrode active material, for example, LiCo a M 1-a O 2 (wherein M is B, Mg, Al, Ti, Mn, V, Fe, Ni, Cu, Zn, Ga, Y, Zr, A lithium cobalt composite oxide represented by at least one selected from Nb, Mo, and In, a satisfying 0 <a ≦ 1, and LiNi b M 1-b O 2 (wherein M Is at least one selected from B, Mg, Al, Ti, Mn, V, Fe, Co, Cu, Zn, Ga, Y, Zr, Nb, Mo, and In, and b is 0 <b ≦ 1 is satisfied.) Can be mentioned. Among these, LiCoO 2 is particularly preferably used in the present invention because it has a large electrochemical capacity and the particle size can be adjusted relatively easily depending on the grinding conditions.

本発明において、固体電解質粒子と正極活物質粉体の混合割合は、重量比（正極活物質粉体：固体電解質粒子）で、５０：５０〜９０：１０の範囲内であることが好ましい。正極活物質粉体の混合割合が少なすぎると、体積エネルギー密度が低下するため好ましくない。正極活物質粉体の混合割合が多すぎると、充分なリチウムイオン導電性を得ることができなくなるため好ましくない。   In the present invention, the mixing ratio of the solid electrolyte particles and the positive electrode active material powder is preferably in the range of 50:50 to 90:10 by weight ratio (positive electrode active material powder: solid electrolyte particles). If the mixing ratio of the positive electrode active material powder is too small, the volume energy density is lowered, which is not preferable. When the mixing ratio of the positive electrode active material powder is too large, it is not preferable because sufficient lithium ion conductivity cannot be obtained.

本発明のリチウム二次電池は、上記本発明の電極からなる正極と、負極と、固体電解質とを備えることを特徴としている。   The lithium secondary battery of the present invention is characterized by comprising a positive electrode comprising the electrode of the present invention, a negative electrode, and a solid electrolyte.

本発明のリチウム二次電池において用いる固体電解質としては、上記本発明の電極に含有させる固体電解質を用いることができる。しかしながら、これに限定されるものではなく、上記電極に含有させる固体電解質と異なる固体電解質を用いてもよい。   As the solid electrolyte used in the lithium secondary battery of the present invention, the solid electrolyte contained in the electrode of the present invention can be used. However, it is not limited to this, You may use the solid electrolyte different from the solid electrolyte contained in the said electrode.

本発明のリチウム二次電池に用いる負極としては、Ｌｉを吸蔵・放出できる物質であればよく、具体例としては、Ｌｉ金属、炭素、Ｌｉと合金化する物質（Ｉｎ、Ｓｉ、Ｓｎ、Ｇｅなど）及びそれら合金の酸化物、窒化物、炭化物などが考えられる。   The negative electrode used in the lithium secondary battery of the present invention may be any material that can occlude / release Li, and specific examples include materials that form an alloy with Li metal, carbon, Li (In, Si, Sn, Ge, etc. And oxides, nitrides and carbides of these alloys.

本発明のリチウム二次電池は、上記本発明の電極からなる正極を用いているので、電気化学容量が高く、かつ充放電サイクル特性に優れた全固体型のリチウム二次電池とすることができる。   Since the lithium secondary battery of the present invention uses the positive electrode comprising the electrode of the present invention, it can be an all-solid-state lithium secondary battery having high electrochemical capacity and excellent charge / discharge cycle characteristics. .

本発明によれば、固体電解質粒子と正極活物質粉末とを均一に分散して混合することができ、これによって電気化学容量を高め、かつ充放電サイクル特性を向上させることができる。   According to the present invention, it is possible to uniformly disperse and mix the solid electrolyte particles and the positive electrode active material powder, thereby increasing the electrochemical capacity and improving the charge / discharge cycle characteristics.

以下、本発明を具体的な実施例により説明するが、本発明は以下の実施例に限定されるものではなく、本発明の要旨を逸脱しない範囲において適宜変更して実施することが可能なものである。   Hereinafter, the present invention will be described by way of specific examples. However, the present invention is not limited to the following examples, and can be appropriately modified and implemented without departing from the scope of the present invention. It is.

（実施例１）
〔正極活物質の作製〕
ＬｉＯＨと、Ｃｏ（ＯＨ）2とを、ＬｉとＣｏのモル比が１：１になるようにらいかい乳鉢にて混合した後、空気雰囲気中で１０００℃で２０時間熱処理した後粉砕し、平均粒子径が約５μｍのＬｉＣｏＯ2粒子を得た。これを再びらいかい乳鉢にて粉砕した。粉砕速度及び粉砕時間を調整することにより、図１に示すような粒度分布を有するＬｉＣｏＯ2粉末活物質を得た。なお、図１に示す粒度分布は、レーザー回折式粒度分布測定装置により測定した。 (Example 1)
[Preparation of positive electrode active material]
LiOH and Co (OH) 2 were mixed in a rough mortar so that the molar ratio of Li and Co was 1: 1, then heat-treated at 1000 ° C. for 20 hours in an air atmosphere, and then pulverized. LiCoO 2 particles having a particle diameter of about 5 μm were obtained. This was again crushed in a rough mortar. By adjusting the grinding speed and grinding time, a LiCoO 2 powder active material having a particle size distribution as shown in FIG. 1 was obtained. The particle size distribution shown in FIG. 1 was measured with a laser diffraction particle size distribution measuring device.

図１から明らかなように、このＬｉＣｏＯ2粉末は、粒子径２μｍ以下及び粒子径３０μｍ以上の粒子を含んでいない。 As apparent from FIG. 1, this LiCoO 2 powder does not contain particles having a particle size of 2 μm or less and a particle size of 30 μm or more.

〔固体電解質の作製〕
Ｌｉ2Ｓ、ＳｉＳ2及びＰ2Ｓ5を、モル比が７１：１６．５：１２．５となるようにめのう乳鉢で混合した後、この混合物１ｇを容積４５ｍｌのＡｌ2Ｏ3製のポットに、直径１０ｍｍのＡｌ2Ｏ3製のボ―ル１０個とともに投入した。この遊星型ボールミル装置を用いて、台盤回転数３７０ｒｐｍで２０時間のメカニカルミリング処理を行うことにより、平均粒子径が約５μｍのガラス試料を得た。得られたガラス試料を、結晶化温度以上である２６０℃で熱処理することにより、Ｌｉ2Ｓ−ＳｉＳ2−Ｐ2Ｓ5のガラス固体電解質を作製した。なお、以上の操作は、全て乾燥アルゴン雰囲気中で行った。 (Production of solid electrolyte)
Li 2 S, SiS 2 and P 2 S 5 were mixed in an agate mortar so that the molar ratio was 71: 16.5: 12.5, and then 1 g of this mixture was added to a 45 ml Al 2 O 3 pot. Were introduced together with 10 balls made of Al 2 O 3 with a diameter of 10 mm. Using this planetary ball mill device, a glass sample having an average particle diameter of about 5 μm was obtained by performing mechanical milling treatment for 20 hours at a platen rotation speed of 370 rpm. The obtained glass sample was heat-treated at 260 ° C., which is equal to or higher than the crystallization temperature, to prepare a Li 2 S—SiS 2 —P 2 S 5 glass solid electrolyte. All the above operations were performed in a dry argon atmosphere.

〔固体電解質含有電極の作製〕
以上のようにして作製した正極活物質粉体と固体電解質粒子とを、重量比（正極活物質粉体：固体電解質粒子）で６０：４０となるように秤量し、めのう乳鉢で混合して、固体電解質含有電極を作製した。 (Production of solid electrolyte-containing electrode)
The positive electrode active material powder and the solid electrolyte particles produced as described above are weighed so that the weight ratio (positive electrode active material powder: solid electrolyte particles) is 60:40, and mixed in an agate mortar. A solid electrolyte-containing electrode was prepared.

図２（ａ）は、以上のようにして作製した固体電解質含有電極のＳＥＭ（走査型電子顕微鏡）像であり、図２（ｂ）は、ＥＰＭＡによる元素（コバルト）分布像であり、図２（ｃ）は、ＥＰＭＡによる元素（硫黄）分布像である。   FIG. 2A is an SEM (scanning electron microscope) image of the solid electrolyte-containing electrode produced as described above, and FIG. 2B is an element (cobalt) distribution image by EPMA. (C) is an element (sulfur) distribution image by EPMA.

図２（ｂ）及び（ｃ）から明らかなように、正極活物質であるＬｉＣｏＯ2粒子と、固体電解質であるＬｉ2Ｓ−ＳｉＳ2−Ｐ2Ｓ5が均一に分散して混合しており、固体電解質と正極活物質の界面が良好に形成されていることがわかる。 As is clear from FIGS. 2B and 2C, the LiCoO 2 particles as the positive electrode active material and the Li 2 S—SiS 2 —P 2 S 5 as the solid electrolyte are uniformly dispersed and mixed. It can be seen that the interface between the solid electrolyte and the positive electrode active material is well formed.

〔試験電池の作製〕
上記の固体電解質含有電極について、可逆的な充放電容量を測定するため、この固体電解質含有電極を用いて試験電池を作製した。 [Production of test battery]
In order to measure reversible charge / discharge capacity of the solid electrolyte-containing electrode, a test battery was produced using the solid electrolyte-containing electrode.

図３は、試験電池作製の工程を示す模式的断面図である。ステンレス棒４の上にポリカーボネートからなる円筒形容器５を載せ、円筒形容器５内に、固体電解質含有電極の粉末２０ｍｇを入れ、次に電極に含有させたのと同じ固体電解質粒子８０ｍｇを入れ、円筒形容器５の上にステンレス棒６を載せた後、このステンレス棒６を３７００ｋｇ／ｃｍ2の圧力で一軸プレスすることにより、直径１０ｍｍの二層ペレットを作製した。その後、ステンレス棒６を取り外し、負極として、厚み０．１ｍｍの金属リチウムをペレットに貼り付け、２５００ｋｇ／ｃｍ2の圧力で再度一軸プレスすることにより、三層ペレットを作製した。ステンレス棒４及び６を上記三層ペレットに接触させ、これを集電体として用い、試験電池とした。 FIG. 3 is a schematic cross-sectional view showing a test battery manufacturing process. A cylindrical container 5 made of polycarbonate is placed on the stainless steel rod 4, and 20 mg of the solid electrolyte-containing electrode powder is placed in the cylindrical container 5, and then 80 mg of the same solid electrolyte particles contained in the electrode are placed. After placing the stainless steel rod 6 on the cylindrical container 5, the stainless steel rod 6 was uniaxially pressed at a pressure of 3700 kg / cm 2 to produce a double-layered pellet having a diameter of 10 mm. Thereafter, the stainless steel rod 6 was removed, metal lithium having a thickness of 0.1 mm was attached to the pellet as the negative electrode, and uniaxial pressing was performed again at a pressure of 2500 kg / cm 2 to produce a three-layer pellet. Stainless steel bars 4 and 6 were brought into contact with the above three-layer pellets and used as current collectors to form test batteries.

〔充放電試験〕
以上のようにして作製した試験電池を用いて、以下の充放電条件で電極特性を測定した。１サイクル目は、Ｌｉ1-xＣｏＯ2において、ｘ＝０．４までリチウムの引き抜きを行う容量規制で充電を行い、放電は２Ｖまでの電位規制で行った。２サイクル目以降は、１サイクル目の充電到達電位と２Ｖの電位範囲で充放電を繰り返した。測定は、温度２５℃、電流密度１２８μＡ／ｃｍ2で行った。 (Charge / discharge test)
Using the test battery produced as described above, the electrode characteristics were measured under the following charge / discharge conditions. In the first cycle, in Li 1-x CoO 2 , charging was performed by capacity regulation in which lithium was extracted until x = 0.4, and discharging was performed by potential regulation up to 2V. From the second cycle onward, charging and discharging were repeated within the potential range of the first cycle charge and 2 V. The measurement was performed at a temperature of 25 ° C. and a current density of 128 μA / cm 2 .

図４に、初期充放電曲線を示す。また、図５に、５０サイクルまでの各サイクルにおける放電容量及び充放電効率を示す。   FIG. 4 shows an initial charge / discharge curve. FIG. 5 shows the discharge capacity and charge / discharge efficiency in each cycle up to 50 cycles.

図４から明らかなように、初期の電気化学容量として８０ｍＡｈ／ｇが得られた。また、図５から明らかなように、１０サイクル目以降の可逆的な電気化学容量は、３８〜４２ｍＡｈ／ｇであり、安定した充放電を行うことができた。   As is clear from FIG. 4, 80 mAh / g was obtained as the initial electrochemical capacity. Further, as is clear from FIG. 5, the reversible electrochemical capacity after the 10th cycle was 38 to 42 mAh / g, and stable charging / discharging could be performed.

（実施例２）
〔正極活物質の作製〕
粉砕速度及び粉砕時間を調整することにより、図６に示すような粒度分布を有する正極活物質粉末とした以外は、実施例１と同様にして正極活物質粉末を作製した。 (Example 2)
[Preparation of positive electrode active material]
A positive electrode active material powder was produced in the same manner as in Example 1 except that the positive electrode active material powder having a particle size distribution as shown in FIG.

図６から明らかなように、本実施例で作製した正極活物質粉末は、３０μｍ以上の粒子を含まないが、２μｍ以下の粒子は含んでいる。   As is clear from FIG. 6, the positive electrode active material powder produced in this example does not contain particles of 30 μm or more, but contains particles of 2 μm or less.

〔固体電解質含有電極の作製〕
上記の正極活物質粉体を用いる以外は、実施例１と同様にして固体電解質含有電極を作製した。 (Production of solid electrolyte-containing electrode)
A solid electrolyte-containing electrode was produced in the same manner as in Example 1 except that the above positive electrode active material powder was used.

図７（ａ）は、この固体電解質含有電極のＳＥＭ像を示しており、図７（ｂ）は、ＥＰＭＡによる元素（コバルト）分布像を示しており、図７（ｃ）は、ＥＰＭＡによる元素（硫黄）分布像を示している。   7A shows an SEM image of this solid electrolyte-containing electrode, FIG. 7B shows an element (cobalt) distribution image by EPMA, and FIG. 7C shows an element by EPMA. (Sulfur) distribution image is shown.

図７（ｂ）及び（ｃ）から明らかなように、正極活物質粉末と固体電解質粒子が互いに均一に分散し、混合されている。実施例１と比較すると、実施例１の方がより均一に分散していることがわかる。   As is clear from FIGS. 7B and 7C, the positive electrode active material powder and the solid electrolyte particles are uniformly dispersed and mixed with each other. Compared to Example 1, it can be seen that Example 1 is more uniformly dispersed.

〔試験電池の作製及び充放電試験〕
上記の固体電解質含有電極を用いる以外は、実施例１と同様にして試験電池を作製し、この試験電池を用いて、実施例１と同様にして充放電試験を行った。 [Production of test battery and charge / discharge test]
A test battery was prepared in the same manner as in Example 1 except that the solid electrolyte-containing electrode was used, and a charge / discharge test was performed in the same manner as in Example 1 using this test battery.

図８は初期充放電曲線を示しており、図９は５０サイクルまでの各サイクルにおける放電容量及び充放電効率を示している。   FIG. 8 shows an initial charge / discharge curve, and FIG. 9 shows the discharge capacity and charge / discharge efficiency in each cycle up to 50 cycles.

図８から明らかなように、初期の電気化学容量として８０ｍＡｈ／ｇが得られた。また、図９から明らかなように、１０サイクル目以降の可逆的な電気化学容量は、１０〜３８ｍＡｈ／ｇであった。   As is clear from FIG. 8, 80 mAh / g was obtained as the initial electrochemical capacity. Further, as is clear from FIG. 9, the reversible electrochemical capacity after the 10th cycle was 10 to 38 mAh / g.

（比較例）
〔正極活物質粉体の作製〕
粉砕速度及び粉砕時間を調整することにより、図１０に示すような粒度分布を有する正極活物質粉体とする以外は、実施例１と同様にして正極活物質粉体を作製した。 (Comparative example)
[Preparation of positive electrode active material powder]
A positive electrode active material powder was prepared in the same manner as in Example 1 except that the positive electrode active material powder having a particle size distribution as shown in FIG. 10 was obtained by adjusting the pulverization speed and pulverization time.

図１０に示すように、ここで得られた正極活物質粉体は粒子径３０μｍ以上の粒子を含んでいる。また、粒子径２μｍ以下の粒子は含まれていない。   As shown in FIG. 10, the positive electrode active material powder obtained here contains particles having a particle diameter of 30 μm or more. Further, particles having a particle diameter of 2 μm or less are not included.

〔固体電解質含有電極の作製〕
上記の正極活物質粉体を用いる以外は、実施例１と同様にして固体電解質含有電極を作製した。 (Production of solid electrolyte-containing electrode)
A solid electrolyte-containing electrode was produced in the same manner as in Example 1 except that the above positive electrode active material powder was used.

図１１（ａ）は、固体電解質含有電極のＳＥＭ像を示しており、図１１（ｂ）は、ＥＰＭＡによる元素（コバルト）分布像を示しており、図１１（ｃ）は、ＥＰＭＡによる元素（硫黄）分布像を示している。   11A shows an SEM image of the solid electrolyte-containing electrode, FIG. 11B shows an element (cobalt) distribution image by EPMA, and FIG. 11C shows an element by EPMA (cobalt). (Sulfur) distribution image.

図１１（ｂ）及び（ｃ）から明らかなように、実施例１（図２）及び実施例２（図７）と比べ、正極活物質粉体及び固体電解質粒子の分散が不均一であることがわかる。   As is clear from FIGS. 11B and 11C, the dispersion of the positive electrode active material powder and the solid electrolyte particles is not uniform as compared with Example 1 (FIG. 2) and Example 2 (FIG. 7). I understand.

〔試験電池の作製及び充放電試験〕
上記の固体電解質含有電極を用いて、実施例１と同様にして試験電池を作製し、この試験電池を用いて、実施例１と同様にして充放電試験を行った。 [Production of test battery and charge / discharge test]
A test battery was produced using the solid electrolyte-containing electrode in the same manner as in Example 1, and a charge / discharge test was conducted in the same manner as in Example 1 using this test battery.

図１２は、初期充放電曲線を示しており、図１３は５０サイクルまでの各サイクルの放電容量及び充放電効率を示している。   FIG. 12 shows an initial charge / discharge curve, and FIG. 13 shows the discharge capacity and charge / discharge efficiency of each cycle up to 50 cycles.

図１２から明らかなように、初期の電気化学容量として６０ｍＡｈ／ｇが得られた。また、図１３から明らかなように、１０サイクル目以降の可逆的な電気化学容量は３〜１０ｍＡｈ／ｇであった。   As is clear from FIG. 12, 60 mAh / g was obtained as the initial electrochemical capacity. Further, as is clear from FIG. 13, the reversible electrochemical capacity after the 10th cycle was 3 to 10 mAh / g.

実施例１及び２と比較例との比較から明らかなように、本発明に従い、粒子径３０μｍ以上の粒子を実質的に含まない正極活物質粉体を用いることにより、高い放電容量を得ることができ、充放電サイクル特性を向上させることができる。   As is clear from the comparison between Examples 1 and 2 and the comparative example, a high discharge capacity can be obtained by using the positive electrode active material powder substantially free of particles having a particle diameter of 30 μm or more according to the present invention. And charge / discharge cycle characteristics can be improved.

本発明に従う実施例１において作製した正極活物質粉体の粒度分布を示す図。The figure which shows the particle size distribution of the positive electrode active material powder produced in Example 1 according to this invention. 本発明に従う実施例１において作製した固体電解質含有電極のＳＥＭ像（ａ）、ＥＰＭＡによる元素（コバルト）分布像（ｂ）、ＥＰＭＡによる元素（硫黄）分布像（ｃ）。The SEM image (a) of the solid electrolyte containing electrode produced in Example 1 according to this invention, the element (cobalt) distribution image (b) by EPMA, and the element (sulfur) distribution image (c) by EPMA. 本発明に従う実施例１において作製した試験電池の作製工程を示す模式的断面図。Typical sectional drawing which shows the preparation process of the test battery produced in Example 1 according to this invention. 本発明に従う実施例１において作製した試験電池の初期充放電曲線を示す図。The figure which shows the initial stage charge / discharge curve of the test battery produced in Example 1 according to this invention. 本発明に従う実施例１において作製した試験電池のサイクル特性を示す図。The figure which shows the cycling characteristics of the test battery produced in Example 1 according to this invention. 本発明に従う実施例２において作製した正極活物質粉体の粒度分布を示す図。The figure which shows the particle size distribution of the positive electrode active material powder produced in Example 2 according to this invention. 本発明に従う実施例２において作製した固体電解質含有電極のＳＥＭ像（ａ）、ＥＰＭＡによる元素（コバルト）分布像（ｂ）、ＥＰＭＡによる元素（硫黄）分布像（ｃ）。The SEM image (a) of the solid electrolyte containing electrode produced in Example 2 according to this invention, the element (cobalt) distribution image (b) by EPMA, and the element (sulfur) distribution image (c) by EPMA. 本発明に従う実施例２において作製した試験電池の初期充放電曲線を示す図。The figure which shows the initial stage charge / discharge curve of the test battery produced in Example 2 according to this invention. 本発明に従う実施例２において作製した試験電池のサイクル特性を示す図。The figure which shows the cycling characteristics of the test battery produced in Example 2 according to this invention. 比較例において作製した正極活物質粉体の粒度分布を示す図。The figure which shows the particle size distribution of the positive electrode active material powder produced in the comparative example. 比較例において作製した固体電解質含有電極のＳＥＭ像（ａ）、ＥＰＭＡによる元素（コバルト）分布像（ｂ）、ＥＰＭＡによる元素（硫黄）分布像（ｃ）。The SEM image (a) of the solid electrolyte containing electrode produced in the comparative example, the element (cobalt) distribution image (b) by EPMA, and the element (sulfur) distribution image (c) by EPMA. 比較例において作製した試験電池の初期充放電曲線を示す図。The figure which shows the initial stage charge / discharge curve of the test battery produced in the comparative example. 比較例において作製した試験電池のサイクル特性を示す図。The figure which shows the cycling characteristics of the test battery produced in the comparative example.

符号の説明Explanation of symbols

１…固体電解質含有電極
２…固体電解質
３…負極
４…ステンレス棒
５…円筒形容器
６…ステンレス棒 DESCRIPTION OF SYMBOLS 1 ... Solid electrolyte containing electrode 2 ... Solid electrolyte 3 ... Negative electrode 4 ... Stainless steel rod 5 ... Cylindrical container 6 ... Stainless steel rod

Claims (5)

リチウム二次電池に用いるリチウムイオン導電性の固体電解質を含有した電極であって、
メカニカルミリング処理により合成したリチウムイオン導電性の固体電解質粒子を、粒子径３０μｍ以上の粒子を実質的に含まない正極活物質粉体に混合して分散させたことを特徴とするリチウム二次電池用固体電解質含有電極。 An electrode containing a lithium ion conductive solid electrolyte used in a lithium secondary battery,
Lithium ion conductive solid electrolyte particles synthesized by mechanical milling treatment are mixed and dispersed in a positive electrode active material powder substantially free of particles having a particle size of 30 μm or more. Solid electrolyte-containing electrode. 前記正極活物質粉体が、粒子径２μｍ以下の粒子を実質的に含まないことを特徴とするリチウム二次電池用固体電解質含有電極。   A solid electrolyte-containing electrode for a lithium secondary battery, wherein the positive electrode active material powder does not substantially contain particles having a particle diameter of 2 μm or less. 前記固体電解質粒子が、Ｌｉ2Ｓ−ＳｉＳ2−Ｐ2Ｓ5であることを特徴とする請求項１または２に記載のリチウム二次電池用固体電解質含有電極。 The solid electrolyte-containing electrode for a lithium secondary battery according to claim 1, wherein the solid electrolyte particles are Li 2 S—SiS 2 —P 2 S 5 . 前記正極活物質粉体が、ＬｉＣｏＯ2であることを特徴とする請求項１〜３のいずれか１項に記載のリチウム二次電池用固体電解質含有電極。 4. The solid electrolyte-containing electrode for a lithium secondary battery according to claim 1, wherein the positive electrode active material powder is LiCoO 2 . 請求項１〜４に記載の電極からなる正極と、負極と、固体電解質とを備えることを特徴とするリチウム二次電池。
A lithium secondary battery comprising a positive electrode comprising the electrode according to claim 1, a negative electrode, and a solid electrolyte.
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