JP2002231225A - Composite electrode material, its manufacturing method, lithium ion secondary electrode negative material using the same, and lithium ion secondary battery - Google Patents
Composite electrode material, its manufacturing method, lithium ion secondary electrode negative material using the same, and lithium ion secondary batteryInfo
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- JP2002231225A JP2002231225A JP2001025426A JP2001025426A JP2002231225A JP 2002231225 A JP2002231225 A JP 2002231225A JP 2001025426 A JP2001025426 A JP 2001025426A JP 2001025426 A JP2001025426 A JP 2001025426A JP 2002231225 A JP2002231225 A JP 2002231225A
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- Prior art keywords
- composite
- electrode material
- electrode
- ion secondary
- composite electrode
- Prior art date
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Classifications
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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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、放電容量、サイク
ル特性に優れたリチウムイオン二次電池の負極材として
好適に用いられる複合電極材料とその製造方法及びこれ
を用いたリチウムイオン二次電池用負極及びリチウムイ
オン二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite electrode material preferably used as a negative electrode material of a lithium ion secondary battery having excellent discharge capacity and cycle characteristics, a method for producing the same, and a lithium ion secondary battery using the same. The present invention relates to a negative electrode and a lithium ion secondary battery.
【０００２】[0002]
【従来の技術】近年、ポータブル機器、電気自動車、電
力貯蔵用として小型、軽量で高エネルギー密度を有する
二次電池に対する要望が高まっている。このような要望
に対し、非水系電解液二次電池、特にリチウムイオン二
次電池はとりわけ高電圧、高エネルギー密度を有する電
池として注目を集めている。2. Description of the Related Art In recent years, there has been an increasing demand for small, lightweight, and high energy density secondary batteries for portable equipment, electric vehicles, and power storage. In response to such demands, non-aqueous electrolyte secondary batteries, particularly lithium ion secondary batteries, have attracted attention as batteries having high voltage and high energy density.
【０００３】リチウムイオン二次電池の負極材料とし
て、金属リチウムは極めて大きな高い充放電容量を実現
可能であるが、その高い反応性のため充放電サイクルの
経過と共に電解液中の溶媒と反応し容量が低下する。ま
た、樹枝状の金属リチウムが生成し易く、正・負極間に
設けられるセパレータを貫通し、短絡を引き起こし易い
という問題点を有している。[0003] As a negative electrode material of a lithium ion secondary battery, metallic lithium can realize an extremely large high charge / discharge capacity, but due to its high reactivity, it reacts with a solvent in an electrolytic solution with the progress of a charge / discharge cycle. Decrease. In addition, there is a problem in that dendritic metallic lithium is easily generated, penetrates a separator provided between the positive electrode and the negative electrode, and easily causes a short circuit.
【０００４】このような問題を解決するため、現行のリ
チウムイオン二次電池の負極材としては低黒鉛化炭素質
材料、高黒鉛化炭素質材料が使用されている。低黒鉛化
炭素質材料は、電解液との反応性が低く、樹枝状金属リ
チウムが生成しづらく、また単位重量当りの放電容量と
して５００Ａｈ／ｋｇ以上の材料が得られているが、真
密度が低いため電極密度を上げられず、このため体積当
りの充放電容量が低くなるという難点を有している。高
黒鉛化炭素質材料は、低黒鉛化炭素質材料と比較して重
量当りの放電容量は３５０〜３７０Ａｈ／ｋｇと低い
が、真密度が高いため電極密度を高くでき、このため体
積当りの放電容量が大きい。また、金属リチウムと比較
して電解液との反応性が低く、樹枝状金属リチウムが生
成しづらく、放電電圧が高く且つ平坦であるという特徴
を有することから、近年、負極用材料として盛んに検討
が為されるようになってきている。In order to solve such a problem, a low graphitized carbonaceous material and a highly graphitized carbonaceous material are used as a negative electrode material of a current lithium ion secondary battery. The low graphitized carbonaceous material has low reactivity with the electrolytic solution, hardly generates dendritic lithium, and has a material with a discharge capacity of 500 Ah / kg or more per unit weight, but the true density is low. The electrode density is too low to increase the electrode density, and the charge / discharge capacity per volume is low. The highly graphitized carbonaceous material has a low discharge capacity per weight of 350 to 370 Ah / kg as compared with the low graphitized carbonaceous material, but has a high true density and can increase the electrode density. Large capacity. In addition, it has low reactivity with electrolytes compared to metallic lithium, has the characteristics of hardly producing dendritic metallic lithium, has a high discharge voltage, and is flat. Is being done.
【０００５】しかしながら、高黒鉛化炭素質材料の放電
容量はリチウムと形成する層間化合物（ＬｉＣ６）によ
って制限（３７２Ａｈ／ｋｇ）されるという課題を有し
ている。この理論容量を超える容量を有する高黒鉛化炭
素質材料の開発が様々な部署で検討されているが、作業
性、サイクル特性を両立したものは未だ見出されていな
い。However, there is a problem that the discharge capacity of the highly graphitized carbonaceous material is limited (372 Ah / kg) by the intercalation compound (LiC 6 ) formed with lithium. The development of highly graphitized carbonaceous materials having a capacity exceeding this theoretical capacity has been studied in various departments, but none of them has been found to achieve both workability and cycle characteristics.
【０００６】低黒鉛化炭素質材料、高黒鉛化炭素質材料
以外の負極材としては珪素、アルミニウム、鉛等の金
属、錫含有酸化物、珪素酸化物などの金属酸化物が高い
放電容量を示すことが知られており、近年、盛んに検討
がなされるようになっている。これらの材料は真密度が
高いため、電極体積当りの放電容量を大きくできるが、
金属系の材料ではリチウムの吸蔵・放出過程での体積変
化が大きく、このため、充放電サイクル経過と伴に放電
容量が著しく低下するという課題を有する。As the negative electrode material other than the low graphitized carbonaceous material and the highly graphitized carbonaceous material, metals such as silicon, aluminum and lead, and metal oxides such as tin-containing oxides and silicon oxides exhibit high discharge capacity. It is known that studies have been actively conducted in recent years. Because these materials have a high true density, the discharge capacity per electrode volume can be increased,
Metal-based materials have a large volume change during the process of inserting and extracting lithium, and therefore have a problem that the discharge capacity is significantly reduced as the charge / discharge cycle progresses.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、高い
放電容量を有し、サイクル特性に優れた複合電極材料と
その製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a composite electrode material having a high discharge capacity and excellent cycle characteristics, and a method for producing the same.
【０００８】本発明の他の目的は、高い放電容量を有
し、サイクル特性に優れた複合電極材料を用いたリチウ
ムイオン二次電池用負極及びリチウムイオン二次電池を
提供することにある。Another object of the present invention is to provide a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using a composite electrode material having a high discharge capacity and excellent cycle characteristics.
【０００９】[0009]
【課題を解決するための手段】本発明は、黒鉛質粒子、
非晶質炭素及び珪素を含有してなり、ＳｉＯ２換算での
珪素含有量が４０〜８０重量％であり、真密度が１．８
×１０３ｋｇ／ｍ３以上、タップ密度が０．８×１０３
ｋｇ／ｍ３以上、比表面積が８×１０３ｍ２／ｋｇ以下
であることを特徴とする複合電極材料に関する。SUMMARY OF THE INVENTION The present invention provides a graphitic particle,
It contains amorphous carbon and silicon, has a silicon content of 40 to 80% by weight in terms of SiO 2 , and has a true density of 1.8.
× 10 3 kg / m 3 or more, tap density 0.8 × 10 3
The present invention relates to a composite electrode material characterized by having a specific surface area of at least 8 kg / m 3 and not more than 8 × 10 3 m 2 / kg.
【００１０】本発明は、また、ＸＰＳのＳｉ２Ｐスペク
トルにおいて、１０２．５〜１０７．５（ｅＶ）付近に
一つのピークを有する上記の複合電極材料に関する。[0010] The present invention also relates to the above composite electrode material having one peak around 102.5 to 107.5 (eV) in a Si2P spectrum of XPS.
【００１１】本発明は、また、黒鉛質粒子含有量が１５
〜５０重量％のとき、金属リチウムを対極として充放電
を行わせたときの放電容量が５００Ａｈ／ｋｇ以上、平
均放電電圧が０．６Ｖ（対金属リチウム）以下である上
記の複合電極材料に関する。[0011] The present invention also relates to the present invention, wherein the content of graphite particles is 15
The present invention relates to the composite electrode material described above, which has a discharge capacity of 500 Ah / kg or more and an average discharge voltage of 0.6 V (vs. lithium metal) or less when charging and discharging are performed using metallic lithium as a counter electrode when the content is about 50% by weight.
【００１２】本発明は、また、金属リチウムを対極とし
て充放電を行わせたときの放電において、ｄＸ／ｄＶ
（Ｘ：放電容量、Ｖ：放電電圧）を放電電圧Ｖに対して
プロットしたグラフ中、０．５Ｖ付近にピークを有しな
い上記の複合電極材料に関する。[0012] The present invention also provides a method for discharging dX / dV in charging and discharging using lithium metal as a counter electrode.
In the graph in which (X: discharge capacity, V: discharge voltage) is plotted against discharge voltage V, the present invention relates to the above composite electrode material having no peak near 0.5 V.
【００１３】本発明は、また、平均粒子径１０μｍ以下
の黒鉛質粒子と有機珪素化合物と炭素前駆体有機高分子
化合物とを混合し、非酸化性雰囲気中で加熱することを
特徴とする複合電極材料の製造方法に関する。The present invention also provides a composite electrode comprising mixing graphite particles having an average particle diameter of 10 μm or less, an organic silicon compound and a carbon precursor organic polymer compound, and heating the mixture in a non-oxidizing atmosphere. The present invention relates to a method for manufacturing a material.
【００１４】本発明は、また、上記の複合電極材料を含
む電極合材を成形してなり、電極合材のかさ密度が１．
２〜１．７×１０３ｋｇ／ｍ３であるリチウムイオン二
次電池用負極に関する。本発明は、また、上記の複合電
極材料を含む電極合材を負極集電体に塗布してなり、電
極合材のかさ密度が１．２〜１．７×１０３ｋｇ／ｍ３
であるリチウムイオン二次電池用負極に関する。According to the present invention, an electrode mixture containing the above-mentioned composite electrode material is molded, and the bulk density of the electrode mixture is 1.
The present invention relates to a negative electrode for a lithium ion secondary battery having a density of 2 to 1.7 × 10 3 kg / m 3 . According to the present invention, an electrode mixture containing the above composite electrode material is applied to a negative electrode current collector, and the bulk density of the electrode mixture is 1.2 to 1.7 × 10 3 kg / m 3.
And a negative electrode for a lithium ion secondary battery.
【００１５】本発明は、また、上記の負極を用いたリチ
ウムイオン二次電池に関する。The present invention also relates to a lithium ion secondary battery using the above-mentioned negative electrode.
【００１６】[0016]
【発明の実施の形態】本発明の複合電極材料は、複合電
極材料粒子中に、黒鉛質粒子、非晶質炭素及びＳｉＯ２
換算で４０〜８０重量％の珪素を含有する。ここでいう
複合とは、黒鉛質粒子と非晶質炭素質粒子の混合物では
なく、複合電極材料粒子一個の中に黒鉛質粒子と非晶質
炭素とが一体化して含まれることを意味し、珪素はこの
複合材料粒子の中に含有される。他の構成、すなわち黒
鉛質粒子と非晶質炭素粒子と珪素の混合物、黒鉛質粒子
と珪素を含有する非晶質炭素粒子などの構成では本発明
のような高い放電容量とサイクル特性は実現されない。BEST MODE FOR CARRYING OUT THE INVENTION The composite electrode material of the present invention contains graphite particles, amorphous carbon and SiO 2 in the composite electrode material particles.
Contains 40 to 80% by weight of silicon in conversion. The composite here means not a mixture of the graphite particles and the amorphous carbon particles, but that the graphite particles and the amorphous carbon are integrally contained in one composite electrode material particle, Silicon is contained in the composite particles. In other configurations, that is, a mixture of graphitic particles, amorphous carbon particles, and silicon, a configuration of graphite particles and amorphous carbon particles containing silicon, etc., the high discharge capacity and cycle characteristics as in the present invention are not realized. .
【００１７】本発明の複合電極材料は、粒子状又は粉末
状（以下両者を粒子状ということがある。）のもので、
好ましくは２００メッシュ以下の粒径の材料として好適
に用いられる。複合電極材料の粒子中に含有される黒鉛
質粒子の数については特に制限はしないが、複数の黒鉛
質粒子を含有させることがサイクル特性を向上させると
いう点が好ましい。The composite electrode material of the present invention is in the form of particles or powder (both are sometimes referred to as particles).
Preferably, it is suitably used as a material having a particle size of 200 mesh or less. Although the number of the graphite particles contained in the particles of the composite electrode material is not particularly limited, it is preferable that the inclusion of a plurality of the graphite particles improves the cycle characteristics.
【００１８】本発明の複合電極材料中に珪素が含有され
ることは、例えば、複合電極材料を蛍光Ｘ線分析によっ
て珪素が認められることによって確認できる。珪素の存
在状態について、本発明の複合電極材料の広角Ｘ線回折
図に珪素含有化合物に該当する明確な回折線が認められ
ないことから、非晶質化合物として存在しているものと
考えられる。The fact that silicon is contained in the composite electrode material of the present invention can be confirmed, for example, by confirming silicon in the composite electrode material by X-ray fluorescence analysis. Regarding the existing state of silicon, since a clear diffraction line corresponding to the silicon-containing compound is not recognized in the wide-angle X-ray diffraction diagram of the composite electrode material of the present invention, it is considered that the compound exists as an amorphous compound.
【００１９】本発明で用いる黒鉛質粒子としては、好ま
しくは平均粒子径２０μｍ以下、より好ましくは平均粒
子径０．１〜１０μｍのものが用いられる。平均粒子径
が２０μｍを超える黒鉛質粒子を用いるとサイクル特
性、放電容量が低下する傾向がある。The graphite particles used in the present invention preferably have an average particle size of 20 μm or less, and more preferably have an average particle size of 0.1 to 10 μm. When graphite particles having an average particle diameter of more than 20 μm are used, the cycle characteristics and discharge capacity tend to decrease.
【００２０】本発明で用いる炭素前駆体有機高分子化合
物としては、石油系、石炭系及び合成ピッチ、タール
類、ポリ塩化ビニル、ポリ塩化ビニリデン、フェノール
樹脂、フラン樹脂、ポリアクリロニトリル、ポリ（α−
ハロゲン化アクリロニトリル）などのアクリル樹脂、ポ
リアミドイミド樹脂、ポリアミド樹脂、ポリイミド樹脂
などを用いることができる。使用量は黒鉛質粒子１００
重量部に対して３０〜９０重量部とすることが好まし
い。The carbon precursor organic high molecular compound used in the present invention includes petroleum, coal and synthetic pitches, tars, polyvinyl chloride, polyvinylidene chloride, phenol resin, furan resin, polyacrylonitrile, poly (α-
An acrylic resin such as halogenated acrylonitrile), a polyamideimide resin, a polyamide resin, a polyimide resin, or the like can be used. The amount used was 100 graphite particles.
It is preferably 30 to 90 parts by weight based on parts by weight.
【００２１】本発明で用いる有機珪素化合物をしては、
シリコンアルコキシド及び／又はその部分縮重合物を用
いることができる。シリコンアルコキシドとしてはテト
ラメトキシシラン、テトラエトキシシラン、テトラプロ
ポキシシラン、トリメトキシメチルシラン、トリエトキ
シメチルシラン等を用いることができる。部分縮重合物
は一般に酸触媒存在下で上記のシリコンアルコキシドを
部分加水分解、縮重合させて作製されるものであり、例
えばテトラメトキシシラン、テトラエトキシシランの部
分縮重合物が容易に入手でき、使用できる。使用量は、
ＳｉＯ２換算での珪素含有量が複合電極材料中に４０〜
８０重量％となる量が用いられる。As the organosilicon compound used in the present invention,
Silicon alkoxide and / or a partially condensed polymer thereof can be used. As the silicon alkoxide, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, trimethoxymethylsilane, triethoxymethylsilane, or the like can be used. The partially condensed polymer is generally prepared by partially hydrolyzing and condensing the above silicon alkoxide in the presence of an acid catalyst, for example, tetramethoxysilane, a partially condensed polymer of tetraethoxysilane can be easily obtained, Can be used. The amount used is
The silicon content in terms of SiO 2 is 40 to 40 in the composite electrode material.
An amount of 80% by weight is used.
【００２２】黒鉛質粒子と有機珪素化合物及び炭素前駆
体有機高分子化合物との混合方法については特に制限し
ないが、特性の優れる複合電極材料を作製するために
は、黒鉛質粒子の表面に、細孔を有する黒鉛質粒子にあ
っては細孔の内部にもこれらの化合物を均一に塗布、浸
透させることが好ましい。これを実現する方法として
は、例えば有機珪素化合物及び炭素前駆体有機高分子化
合物を溶媒を用いて溶液とし、この溶液に黒鉛質粒子を
分散、混合し、次いで溶媒を除去することによって黒鉛
質粒子と有機珪素化合物及び炭素前駆体有機高分子化合
物の均一な混合物を得ることができる。用いる溶媒は有
機珪素化合物及び炭素前駆体有機高分子化合物を共に溶
解できるものであれば特に制限なく使用できる。The method of mixing the graphite particles with the organosilicon compound and the carbon precursor organic polymer compound is not particularly limited. However, in order to produce a composite electrode material having excellent characteristics, the surface of the graphite particles is coated with fine particles. In the case of graphite particles having pores, it is preferable to uniformly apply and penetrate these compounds even inside the pores. As a method of realizing this, for example, an organic silicon compound and a carbon precursor organic polymer compound are made into a solution using a solvent, and the graphite particles are dispersed and mixed in the solution, and then the graphite particles are removed by removing the solvent. And a homogeneous mixture of the organic silicon compound and the carbon precursor organic polymer compound. The solvent used is not particularly limited as long as it can dissolve both the organic silicon compound and the carbon precursor organic polymer compound.
【００２３】得られた黒鉛質粒子と有機珪素化合物及び
炭素前駆体有機高分子化合物の混合物は、次の加熱工程
に先立って平均粒子径１００μｍ以下まで粉砕すること
が好ましい。この粉砕には振動ミル、カッターミル、ピ
ンミル、ハンマーミル、ジェットミル等の公知の機械的
粉砕装置が使用できる。また、さらに風力式、機械式等
の分級機を用いて分級処理を行っても良い。It is preferable that the obtained mixture of the graphitic particles, the organic silicon compound and the carbon precursor organic polymer compound is pulverized to an average particle diameter of 100 μm or less prior to the next heating step. For this pulverization, a known mechanical pulverizer such as a vibration mill, a cutter mill, a pin mill, a hammer mill, and a jet mill can be used. Classification may be further performed using a classifier such as a wind-type or mechanical classifier.
【００２４】本発明の複合電極材料の特性として、真密
度が１．８×１０３ｋｇ／ｍ３以上、タップ密度が０．
８×１０３ｋｇ／ｍ３以上、比表面積が８×１０３ｍ２
／ｋｇ以下であることが必要である。このような特性
は、珪素を含むことにより達成することができるが、黒
鉛と炭素の複合材に粉末及びバルクの珪素を混合しただ
けでは達成できない。すなわち、黒鉛質粒子に有機珪素
化合物及び炭素前駆体と混合し、加熱によって有機珪素
化合物、炭素前駆体をそれぞれ分解、炭素化することが
重要である。As characteristics of the composite electrode material of the present invention, the true density is 1.8 × 10 3 kg / m 3 or more, and the tap density is 0.1 kg / m 3 .
8 × 10 3 kg / m 3 or more, specific surface area of 8 × 10 3 m 2
/ Kg or less. Such characteristics can be achieved by including silicon, but cannot be achieved only by mixing powder and bulk silicon with a composite material of graphite and carbon. That is, it is important to mix the graphitic particles with the organic silicon compound and the carbon precursor, and to decompose and carbonize the organic silicon compound and the carbon precursor, respectively, by heating.
【００２５】また、Ｘ線光電子分光法（ＸＰＳ）のＳｉ
２Ｐスペクトルは、１０２．５〜１０７．５（ｅＶ）付
近に一つのピークを示す。このようなピークは、炭素と
黒鉛の複合体に珪素粉末を混合した場合では得られな
く、本発明の特長である。本発明の複合電極材料は、放
電容量が５００Ａｈ／ｋｇ以上、平均放電電圧が０．６
Ｖ（対金属リチウム）以下という充放電特性を示す。こ
のような特性は、黒鉛質粒子及び非晶質炭素からなり黒
鉛質粒子１５〜５０重量％を含む複合電極材料に珪素を
ＳｉＯ２換算で４０〜８０重量％含有させることにより
達成される。しかし、黒鉛質粒子含有量及び珪素含有量
がこの範囲外の試料では、平均放電電圧が０．６Ｖ（対
金属リチウム）以下になる可能性があるが、放電容量が
５００Ａｈ／ｋｇ以上の特性は実現されない。さらに上
記に示す有機珪素化合物と炭素前駆体を使用しない場
合、このような充放電特性が実現されない。また、本発
明の複合電極材料は、金属リチウムを対極として充放電
を行わせた時の放電において、ｄＸ／ｄＶ（Ｘ：放電容
量、Ｖ：放電電圧）を放電電圧Ｖに対してプロットした
グラフ中、０．５Ｖ付近にピークを有しない。この０．
５Ｖ付近のピークは、金属珪素あるいはＳｉＯを含む黒
鉛−炭素複合材において観察されるもので、このような
複合材を負極材料として用いた場合、サイクルに伴う放
電容量の低下が大きくなる。In addition, X-ray photoelectron spectroscopy (XPS)
The 2P spectrum shows one peak around 102.5 to 107.5 (eV). Such a peak cannot be obtained when silicon powder is mixed with a composite of carbon and graphite, and is a feature of the present invention. The composite electrode material of the present invention has a discharge capacity of 500 Ah / kg or more and an average discharge voltage of 0.6.
It shows charge / discharge characteristics of V (vs. metallic lithium) or less. Such properties are achieved by the silicon composite electrode material containing 15 to 50 wt% graphite particles consist graphite particles and amorphous carbon containing 40 to 80 wt% in terms of SiO 2. However, in a sample in which the content of graphite particles and the content of silicon are out of these ranges, the average discharge voltage may be 0.6 V (vs. lithium metal) or less. Not realized. Further, when the organic silicon compound and the carbon precursor shown above are not used, such charge / discharge characteristics cannot be realized. Further, the composite electrode material of the present invention is a graph in which dX / dV (X: discharge capacity, V: discharge voltage) is plotted with respect to discharge voltage V in discharge when charging and discharging are performed using metallic lithium as a counter electrode. Medium, no peak around 0.5V. This 0.
The peak around 5 V is observed in a graphite-carbon composite material containing metallic silicon or SiO. When such a composite material is used as a negative electrode material, the decrease in discharge capacity accompanying a cycle becomes large.
【００２６】得られた黒鉛質粒子と有機珪素化合物及び
炭素前駆体有機高分子化合物の混合物を９００〜１４０
０℃、非酸化性雰囲気中で加熱する。炭素化温度が９０
０℃未満では不可逆容量が大きくなる傾向がある。一
方、炭素化温度が１５００℃を超えると、有機珪素化合
物分解生成物と炭素及び／或いは黒鉛質粒子との反応が
激しく起こり、広角Ｘ線回折図には炭化珪素の回折線が
認められるようになり、電極材料として用いた場合、放
電容量が著しく低下する傾向がある。炭素化の際の非酸
化性雰囲気としては、窒素雰囲気、不活性雰囲気、真空
雰囲気等が使用できる。得られた複合電極材料を公知の
機械的粉砕装置を用いて解砕、更に分級することができ
る。得られた複合電極材料の平均粒子径は１〜６０μｍ
の範囲とすることが好ましい。平均粒子径が６０μｍを
超えると電極表面に凸凹が発生し易くなり、好ましくな
く、一方平均粒子径が１μｍを下回る場合、不可逆容量
が大きくなるため好ましくない。A mixture of the obtained graphitic particles, an organic silicon compound and a carbon precursor organic high molecular compound was used in an amount of 900 to 140.
Heat at 0 ° C. in a non-oxidizing atmosphere. Carbonization temperature of 90
Below 0 ° C., the irreversible capacity tends to increase. On the other hand, when the carbonization temperature exceeds 1500 ° C., the reaction between the decomposition product of the organosilicon compound and the carbon and / or graphitic particles occurs violently, and the wide-angle X-ray diffraction diagram shows that the diffraction line of silicon carbide is recognized. When used as an electrode material, the discharge capacity tends to be significantly reduced. As the non-oxidizing atmosphere at the time of carbonization, a nitrogen atmosphere, an inert atmosphere, a vacuum atmosphere, or the like can be used. The obtained composite electrode material can be crushed and classified using a known mechanical crushing device. The average particle diameter of the obtained composite electrode material is 1 to 60 μm.
It is preferable to be within the range. If the average particle diameter exceeds 60 μm, irregularities are likely to be generated on the electrode surface, which is not preferable. On the other hand, if the average particle diameter is less than 1 μm, the irreversible capacity increases, which is not preferable.
【００２７】本発明の複合電極材料は、例えば以下のよ
うにしてリチウムイオン二次電池用電極とすることがで
きる。The composite electrode material of the present invention can be used as an electrode for a lithium ion secondary battery, for example, as follows.
【００２８】本発明の複合電極材料は、有機高分子結着
剤と混合し、次いで電極の形状に成形される。有機高分
子結着剤としては、ポリエチレン、ポリプロピレン、ポ
リエチレンテレフタレート、芳香族ポリアミド、芳香族
ポリイミド、セルロース、ポリ弗化ビニリデン、ポリテ
トラフルオロエチレン、テトラフルオロエチレンを含む
共重合フッ素ポリマーなどの樹枝状高分子材料、スチレ
ン・ブタジエンゴム、イソプレンゴム、ブタジエンゴ
ム、エチレン・プロピレンゴム等のゴム状高分子材料、
エチレン・酢酸ビニル共重合体、プロピレン・α−オレ
フィン共重合体等の軟質樹枝状高分子材料、ポリエチレ
ンオキサイド、ポリプロピレンオキサイド、ポリエピク
ロロヒドリン、ポリファゼン、ポリ弗化ビニリデン、ポ
リアクリロニトリル等の有機高分子材料にリチウム塩又
はリチウムを主体とするアルカリ金属塩を複合化した系
等のイオン導電性高分子材料を用いることができる。こ
れらの有機高分子結着剤の他に、粘度調整剤としてカル
ボキシメチルセルロース、ポリアクリル酸ソーダ、その
他のアクリル系ポリマー等を添加しても良い。これらの
有機高分子結着剤と本発明の複合電極材料との混合割合
は、複合電極材料１００重量部に対して結着剤が０．１
〜３０重量部、より好ましくは０．５〜２０重量部、さ
らに好ましくは１〜１５重量部である。The composite electrode material of the present invention is mixed with an organic polymer binder and then formed into an electrode shape. Organic polymer binders include dendritic polymers such as polyethylene, polypropylene, polyethylene terephthalate, aromatic polyamide, aromatic polyimide, cellulose, polyvinylidene fluoride, polytetrafluoroethylene, and copolymerized fluoropolymers including tetrafluoroethylene. Molecular materials, styrene-butadiene rubber, isoprene rubber, butadiene rubber, rubber-like polymer materials such as ethylene-propylene rubber,
Soft dendritic polymer materials such as ethylene / vinyl acetate copolymer and propylene / α-olefin copolymer, and organic high-density materials such as polyethylene oxide, polypropylene oxide, polyepichlorohydrin, polyphazene, polyvinylidene fluoride, and polyacrylonitrile. An ion conductive polymer material such as a system in which a lithium salt or a lithium-based alkali metal salt is complexed with a molecular material can be used. In addition to these organic polymer binders, carboxymethyl cellulose, sodium polyacrylate, other acrylic polymers and the like may be added as a viscosity modifier. The mixing ratio of the organic polymer binder and the composite electrode material of the present invention was such that the binder was 0.1 parts by weight with respect to 100 parts by weight of the composite electrode material.
The amount is from 30 to 30 parts by weight, more preferably from 0.5 to 20 parts by weight, even more preferably from 1 to 15 parts by weight.
【００２９】本発明の複合電極材料粉末を上記の有機高
分子結着剤と混合し、そのままロール成形、圧縮成形な
どの方法で電極の形状に成形して、電極成形体を作製す
ることができる。電極成形体における電極合材のかさ密
度は、１．２〜１．７×１０ ３ｋｇ／ｍ３であることが
好ましい。かさ密度が１．２×１０３ｋｇ／ｍ３未満の
場合は充放電サイクル経過に伴う放電容量の低下が大き
くなる傾向が見られる。一方、かさ密度が１．７×１０
３ｋｇ／ｍ３を超える場合には、電極合材中の電解液の
浸透に長時間を要する、成形時に集電体に切れが発生し
やすくなる等の問題が生じ好ましくない。また、本発明
の複合電極材料粉末と上記の有機高分子結着剤の混合物
を溶媒中に分散させ、スラリーとし、これを金属製の集
電体等に塗布しても良い。集電体金属としては、圧延銅
箔、電解銅箔、パンチング銅箔、ニッケル箔等が用いら
れる。電極成形体の形状は、シート状、ペレット状等、
任意に設定できる。このようにして得られた電極成形体
を用いて電池を組み立てるが、これに先立って或いは組
み立ての際に活物質であるリチウム金属を電極成形体に
担持させることができる。これにより初回充電時の不可
逆容量が大幅に低減できる。この担持方法としては化学
的方法、物理的方法、電気科学的方法があり、例えばリ
チウムイオン含有電解液に電極成形体を浸漬し、対極に
金属リチウムを用いて電気含浸する方法、電極成形体作
製時に金属リチウム粉末を混合する方法、金属リチウム
と電極成形体を電気的に接触させる方法等がある。The composite electrode material powder of the present invention is prepared using the above organic high
Mix with molecular binder, roll forming, compression molding
What method is used to form the electrode
Can be Density of electrode mixture in electrode compact
The degree is 1.2-1.7 × 10 3kg / m3That it is
preferable. Bulk density is 1.2 × 103kg / m3Less than
In this case, the discharge capacity greatly decreases with the progress
There is a tendency to be. On the other hand, the bulk density is 1.7 × 10
3kg / m3Exceeds the electrolyte solution in the electrode mixture.
It takes a long time to penetrate.
This is not preferred because of problems such as increased ease of use. In addition, the present invention
Of the composite electrode material powder and the organic polymer binder described above
Is dispersed in a solvent to form a slurry.
It may be applied to an electric body or the like. Rolled copper as the current collector metal
Foil, electrolytic copper foil, punched copper foil, nickel foil, etc.
It is. The shape of the electrode molded body is a sheet shape, a pellet shape, etc.
Can be set arbitrarily. Electrode molded body thus obtained
Assemble the battery using
At the time of vertical setting, lithium metal, which is the active material, is
It can be carried. This makes it impossible at the time of first charging
The reverse capacity can be greatly reduced. This loading method is chemical
Methods, physical methods, and electrochemical methods.
Immerse the electrode compact in an electrolyte containing t
Method of electro-impregnation using lithium metal, electrode molding
Method of mixing metallic lithium powder during production, metallic lithium
And an electrode molded body are electrically contacted.
【００３０】以上のようにして作製された電極成形体
は、セパレータを介して正極と対向して配置され、リチ
ウム二次電池を構成する。The electrode formed body manufactured as described above is disposed so as to face the positive electrode with the separator interposed therebetween, and forms a lithium secondary battery.
【００３１】正極材料としては、特に限定しないが、例
えばバナジウム酸化物、バナジウム硫化物、モリブデン
酸化物、モリブデン硫化物、マンガン酸化物、マンガン
硫化物、クロム酸化物、チタン酸化物、チタン硫化物、
これらの複合酸化物、複合硫化物等の金属カルコゲン化
合物、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、ＬｉＭｎＯ３）、リチウム
ニッケルコバルト酸化物｛ＬｉｘＮｉｙＣｏ（ １−ｙ）
Ｏ２｝等の複合酸化物、これらに他の金属元素（Ａｌ、
Ｆｅ、Ｍｎ、Ｍｇ、Ｃｏ等）を添加した複合酸化物等を
用いることができる。また、ポリアニリン、ポリピロー
ル等の導電性ポリマーを用いることもできる。The material of the positive electrode is not particularly limited. For example, vanadium oxide, vanadium sulfide, molybdenum oxide, molybdenum sulfide, manganese oxide, manganese sulfide, chromium oxide, titanium oxide, titanium sulfide,
Metal chalcogen compounds such as composite oxides and composite sulfides, lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), lithium manganese oxide (LiMn 2 O 4 , LiMnO 3 ), lithium nickel cobalt Oxide @Li x Ni y Co ( 1-y)
Composite oxides such as O 2 、, and other metal elements (Al,
A composite oxide or the like to which Fe, Mn, Mg, Co, or the like is added can be used. Further, a conductive polymer such as polyaniline or polypyrrole can also be used.
【００３２】電解液としては、非水系溶媒に電解質とな
るリチウム塩を溶解したものを用いる。電解質として
は、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＢ
Ｆ４、ＬｉＳＯ３ＣＦ３、ＬｉＮ（ＳＯ２ＣＦ３）２等
のリチウム金属塩、テトラアルキルアンモニウム塩等を
用いることができる。リチウム塩の濃度は０．２〜２ｍ
ｏｌ／ｌが好ましく、より好ましくは０．３〜１．９ｍ
ｏｌ／ｌである。非水系溶媒としては、プロピレンカー
ボネート、エチレンカーボネート、ブチレンカーボネー
ト、ビニレンカーボネート、γ−ブチロラクトン等の環
状エステル類、ジエチルカーボネート等の鎖状エステル
類、メチルエチルケトン等のケトン類、１，２−ジメト
キシエタン、ジオキソラン、テトラヒドロフラン、１，
２−ジメチルテトラヒドロフラン、クラウンエーテル等
のエーテル類を用いることができる。また、上記塩類を
ポリエチレンオキサイド、ポリホスファゼン、ポリアジ
リジン、ポリアクリロニトリル、ポリエチレンスルフィ
ド等やこれらの誘導体、混合物、複合体等に混合された
固体電解質を用いこと事もできる。この場合、固体電解
質はセパレータも兼ねることができ、セパレータは不要
となる、As the electrolytic solution, a solution in which a lithium salt serving as an electrolyte is dissolved in a non-aqueous solvent is used. As the electrolyte, LiClO 4, LiPF 6, LiAsF 6, LiB
A lithium metal salt such as F 4 , LiSO 3 CF 3 , and LiN (SO 2 CF 3 ) 2 , a tetraalkylammonium salt, and the like can be used. The concentration of lithium salt is 0.2-2m
ol / l is preferable, and more preferably 0.3 to 1.9 m
ol / l. Non-aqueous solvents include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, cyclic esters such as γ-butyrolactone, chain esters such as diethyl carbonate, ketones such as methyl ethyl ketone, 1,2-dimethoxyethane, dioxolane , Tetrahydrofuran, 1,
Ethers such as 2-dimethyltetrahydrofuran and crown ether can be used. Further, a solid electrolyte in which the above salts are mixed with polyethylene oxide, polyphosphazene, polyaziridine, polyacrylonitrile, polyethylene sulfide or the like, or a derivative, mixture, or composite thereof can also be used. In this case, the solid electrolyte can also serve as a separator, and the separator is not required.
【００３３】負極と正極を分離し、電解液を保持するセ
パレータとしては、ポリエチレン、ポリプロピレン、ポ
リプロピレン／ポリプロピレン複合系、ポリプロピレン
／フッ素樹脂複合系等の微多孔質膜、不織布等を使用す
ることができる。As the separator for separating the negative electrode and the positive electrode and holding the electrolyte, a microporous membrane such as polyethylene, polypropylene, a polypropylene / polypropylene composite system, a polypropylene / fluororesin composite system, a nonwoven fabric, or the like can be used. .
【００３４】[0034]
【実施例】以下、実施例を用いて本発明を更に説明する
が、本発明はこれに限定されるものではない。EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.
【００３５】実施例１ フラン樹脂（ＶＦ３０３ 日立化成工業（株）製、液
状）１．２ｋｇとテトラメトキシシラン部分縮重合物
（Ｍ−シリケート５１ 多摩化学工業（株）製、液状）
２．４ｋｇを混合した。次いで、混合器に黒鉛質粒子
（平均粒子径：約５．７μｍ、性状：凸凹状の楕円形、
平均粒径（５０％径）：約０．７μｍ ＫＳ６ＴＩＭＥ
Ｘ製）０．６ｋｇを入れた後、上記の混合物を加えて、
一時間おきに５０℃、６０℃、７０℃、８０℃、１００
℃、１２０℃と温度を上げながら混合した。得られた複
合体粉末を空気中、３℃／ｍｉｎの速度で２５０℃まで
昇温し、１時間保持した。次いで、窒素気流中、２０℃
／時間の速度で９００℃まで昇温し、１時間保持して炭
素前駆体（フラン樹脂）、有機珪素化合物（テトラメト
キシシラン部分縮重合物）を炭素化、分解して、黒鉛質
粒子、非晶質炭素及び珪素を含有する複合体を得た。さ
らに、窒素雰囲気で１３００℃、１時間焼成した。これ
をカッターミルで解砕し、２００ｍｅｓｈ以下の複合体
粉末とした。得られた複合体粉末（複合電極材料）につ
いて、蛍光Ｘ線分析により珪素含有量を測定したとこ
ろ、５２重量％であった。また、黒鉛含有量は２６重量
％であった。複合体粉末の物性は、かさ密度０．８７×
１０３ｋｇ／ｍ３、タップ密度１．３１×１０３ｋｇ／
ｍ３、真密度１．９６×１０３ｋｇ／ｍ３、比表面積
３．５×１０３ｍ２／ｋｇであった。Example 1 1.2 kg of a furan resin (VF303, manufactured by Hitachi Chemical Co., Ltd., liquid) and a partially condensed polymer of tetramethoxysilane (M-silicate 51, manufactured by Tama Chemical Industry Co., Ltd., liquid)
2.4 kg were mixed. Next, the graphite particles (average particle diameter: about 5.7 μm, properties: uneven ellipsoid,
Average particle size (50% diameter): about 0.7 μm KS6TIME
X)), and after adding 0.6 kg, the above mixture was added.
50 ° C, 60 ° C, 70 ° C, 80 ° C, 100
C. and 120.degree. C. while increasing the temperature. The obtained composite powder was heated in the air to 250 ° C. at a rate of 3 ° C./min and kept for 1 hour. Then, at 20 ° C in a nitrogen stream.
The temperature was raised to 900 ° C. at a rate of / hour, and the temperature was maintained for 1 hour to carbonize and decompose the carbon precursor (furan resin) and the organosilicon compound (tetramethoxysilane partially condensed polymerized product). A composite containing crystalline carbon and silicon was obtained. Further, firing was performed at 1300 ° C. for 1 hour in a nitrogen atmosphere. This was crushed by a cutter mill to obtain a composite powder of 200 mesh or less. When the silicon content of the obtained composite powder (composite electrode material) was measured by fluorescent X-ray analysis, it was 52% by weight. The graphite content was 26% by weight. The physical properties of the composite powder are bulk density 0.87x
10 3 kg / m 3 , tap density 1.31 × 10 3 kg /
m 3 , true density 1.96 × 10 3 kg / m 3 , specific surface area 3.5 × 10 3 m 2 / kg.
【００３６】実施例２ フラン樹脂０．８ｋｇ、テトラメトキシシラン部分縮重
合物２．４ｋｇ、黒鉛質粒子０．４ｋｇを実施例１と同
様にして複合体粉末を作製した。得られた複合体粉末の
珪素含有量は６１重量％、黒鉛含有量は２１重量％であ
った。複合体粉末の物性は、かさ密度０．５８×１０３
ｋｇ／ｍ３、タップ密度１．１８×１０３ｋｇ／ｍ３、
真密度２．０２×１０３ｋｇ／ｍ３、比表面積４．４×
１０３ｍ２／ｋｇであった。Example 2 A composite powder was prepared in the same manner as in Example 1 except that 0.8 kg of a furan resin, 2.4 kg of a partially condensed polymer of tetramethoxysilane, and 0.4 kg of graphite particles were used. The obtained composite powder had a silicon content of 61% by weight and a graphite content of 21% by weight. The physical properties of the composite powder are as follows: bulk density 0.58 × 10 3
kg / m 3 , tap density 1.18 × 10 3 kg / m 3 ,
True density 2.02 × 10 3 kg / m 3 , specific surface area 4.4 ×
It was 10 3 m 2 / kg.
【００３７】実施例３ フラン樹脂０．４ｋｇ、テトラメトキシシラン部分縮重
合物２．４ｋｇ、黒鉛質粒子０．２ｋｇを実施例１と同
様にして複合体粉末を作製した。得られた複合体粉末の
珪素含有量は７６重量％、黒鉛含有量は１３重量％であ
った。複合体粉末の物性は、かさ密度０．６６×１０３
ｋｇ／ｍ３、タップ密度１．２３×１０３ｋｇ／ｍ３、
真密度２．１６×１０３ｋｇ／ｍ３、比表面積４．２×
１０３ｍ２／ｋｇであった。Example 3 A composite powder was prepared in the same manner as in Example 1 except that 0.4 kg of a furan resin, 2.4 kg of a partially condensed polymer of tetramethoxysilane, and 0.2 kg of graphite particles were used. The obtained composite powder had a silicon content of 76% by weight and a graphite content of 13% by weight. The physical properties of the composite powder are as follows: bulk density: 0.66 × 10 3
kg / m 3 , tap density 1.23 × 10 3 kg / m 3 ,
True density 2.16 × 10 3 kg / m 3 , specific surface area 4.2 ×
It was 10 3 m 2 / kg.
【００３８】実施例４ フラン樹脂１．２ｋｇ、テトラメトキシシラン部分縮重
合物２．１ｋｇ、黒鉛質粒子０．６ｋｇを実施例１と同
様にして複合体粉末を作製した。得られた複合体粉末の
珪素含有量は７０重量％、黒鉛含有量は２８重量％であ
った。複合体粉末の物性は、かさ密度０．４８×１０３
ｋｇ／ｍ３、タップ密度０．９４×１０３ｋｇ／ｍ３、
真密度１．８２×１０３ｋｇ／ｍ３、比表面積３．７×
１０３ｍ２／ｋｇであった。Example 4 A composite powder was prepared in the same manner as in Example 1 except that 1.2 kg of a furan resin, 2.1 kg of a partially condensed tetramethoxysilane polymer, and 0.6 kg of graphite particles were used. The obtained composite powder had a silicon content of 70% by weight and a graphite content of 28% by weight. The physical properties of the composite powder are as follows: bulk density 0.48 × 10 3
kg / m 3 , tap density 0.94 × 10 3 kg / m 3 ,
True density 1.82 × 10 3 kg / m 3 , specific surface area 3.7 ×
It was 10 3 m 2 / kg.
【００３９】比較例１ 珪素化合物であるテトラメトキシシラン部分縮重合物を
用いずにフラン樹脂１．９６ｋｇと黒鉛質粒子０．９８
ｋｇで実施例１と同様にして複合体粉末を作製した。得
られた複合体粉末の珪素含有量は、珪素化合物を含まな
いので０重量％である。黒鉛含有量は５６重量％であ
る。複合体粉末の物性は、かさ密度０．３０×１０３ｋ
ｇ／ｍ３、タップ密度０．９２×１０３ｋｇ／ｍ３、真
密度１．５１×１０３ｋｇ／ｍ３、比表面積５．２×１
０３ｍ２／ｋｇであった。Comparative Example 1 1.96 kg of a furan resin and 0.98 of graphitic particles were used without using a tetramethoxysilane partial condensation polymer as a silicon compound.
A composite powder was produced in the same manner as in Example 1 with kg. The silicon content of the obtained composite powder is 0% by weight because no silicon compound is contained. The graphite content is 56% by weight. The physical properties of the composite powder are as follows: bulk density: 0.30 × 10 3 k
g / m 3 , tap density 0.92 × 10 3 kg / m 3 , true density 1.51 × 10 3 kg / m 3 , specific surface area 5.2 × 1
0 was 3 m 2 / kg.
【００４０】比較例２ フラン樹脂１．０ｋｇ、テトラメトキシシラン部分縮重
合物０．２ｇ、黒鉛質粒子１．０ｋｇを実施例１と同様
にして複合体粉末を作製した。得られた複合体粉末の珪
素含有量は２５重量％、黒鉛含有量は６５重量％であっ
た。複合体粉末の物性は、かさ密度０．５２×１０３ｋ
ｇ／ｍ３、タップ密度１．０２×１０３ｋｇ／ｍ３、真
密度１．７２×１０３ｋｇ／ｍ３、比表面積８．２×１
０３ｍ２／ｋｇであった。Comparative Example 2 A composite powder was prepared in the same manner as in Example 1 except that 1.0 kg of a furan resin, 0.2 g of a partially condensed polymer of tetramethoxysilane, and 1.0 kg of graphite particles were used. The silicon content of the obtained composite powder was 25% by weight, and the graphite content was 65% by weight. The physical properties of the composite powder are as follows: bulk density 0.52 × 10 3 k
g / m 3 , tap density 1.02 × 10 3 kg / m 3 , true density 1.72 × 10 3 kg / m 3 , specific surface area 8.2 × 1
0 was 3 m 2 / kg.
【００４１】比較例３ フラン樹脂１．５ｋｇ、テトラメトキシシラン部分縮重
合物１．５ｋｇを実施例１と同様にして複合体粉末を作
製した。得られた複合体粉末の珪素含有量は５６重量
％、黒鉛含有量は０重量％であった。複合体粉末の物性
は、かさ密度０．７４×１０３ｋｇ／ｍ３、タップ密度
１．１５×１０３ｋｇ／ｍ３、真密度１．９３×１０３
ｋｇ／ｍ３、比表面積３．２×１０３ｍ２／ｋｇであっ
た。Comparative Example 3 A composite powder was prepared in the same manner as in Example 1 except that 1.5 kg of a furan resin and 1.5 kg of a partially condensed polymer of tetramethoxysilane were used. The obtained composite powder had a silicon content of 56% by weight and a graphite content of 0% by weight. The physical properties of the composite powder were as follows: bulk density 0.74 × 10 3 kg / m 3 , tap density 1.15 × 10 3 kg / m 3 , and true density 1.93 × 10 3
kg / m 3 and a specific surface area of 3.2 × 10 3 m 2 / kg.
【００４２】実施例１〜４と比較例１〜３で示した複合
体粉末の充放電試験を行った。電極作製方法は、充放電
試験の方法は、得られた複合体粉末９０重量％に、Ｎ−
メチル−２−ピロリドンに溶解したポリ弗化ビニリデン
を固形分で１０重量％添加、混練しスラリーを作製し
た。このスラリーを厚さ１０μｍの圧延銅箔に塗布し、
更に乾燥した後、１９．６ＭＰａ（２００×１０４ｋｇ
ｆ／ｍ２）の圧力でプレスし負極とした。充放電試験方
法は、対極、参照極を金属Ｌｉ、電解液を１ＭのＬｉＰ
Ｆ６ を溶解した、エチレンカーボネート／ジメチルカ
ーボネート（３／７）溶液、セパレータをポリエチレン
微多孔質膜、充放電電流を０．２ｍＡ、充電をＣＣ／Ｃ
Ｖ充電、放電をＣＣ放電、カットオフ電圧を１．５Ｖ
（対金属Ｌｉ）で行った。充放電試験の設定は、ＣＣ／
ＣＶ充電：０．２ｍＡで０．２Ｖ（対金属Ｌｉ）まで充
電後、０．２Ｖで電流値が０．０１ｍＡまで充電する、
ＣＣ放電：０．２ｍＡで１．５Ｖまで放電する。表１に
上記に示した実施例１〜４、比較例１〜３の電極かさ密
度、１サイクル目の放電容量と充放電効率、５０サイク
ル後での放電容量、平均放電電圧を示す。このように黒
鉛質粒子、有機珪素化合物、炭素前駆体の３つを複合化
し、さらに珪素含有量が４０〜８０重量％でないと、サ
イクル性が向上しない。また、電極かさ密度を１．５〜
１．６ｇ／ｃｍ３に上げても、高い放電容量を有し、サ
イクル性も維持できる。しかし、黒鉛質粒子、有機珪素
化合物、炭素前駆体のいずれか１つか不足する場合、又
は珪素含有量が４０〜８０重量％でない場合、電極かさ
蜜度、放電容量、サイクル性に問題が生じる。The composite powders shown in Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to charge / discharge tests. The electrode was prepared by a charge / discharge test method in which 90% by weight of the obtained composite powder was added to N-
Polyvinylidene fluoride dissolved in methyl-2-pyrrolidone was added at 10% by weight in solid content and kneaded to prepare a slurry. This slurry is applied to a 10 μm-thick rolled copper foil,
After further drying, 19.6 MPa (200 × 10 4 kg
f / m 2) Press to obtain a negative electrode. The charge / discharge test method is such that the counter electrode and the reference electrode are metallic Li, and the electrolytic solution is 1M LiP.
Was dissolved F 6, ethylene carbonate / dimethyl carbonate (3/7) solution, a microporous polyethylene membrane separator, charging and discharging current 0.2 mA, a charge CC / C
V charge, discharge CC discharge, cutoff voltage 1.5V
(With respect to metal Li). The charge / discharge test setting is CC /
CV charging: After charging at 0.2 mA to 0.2 V (to metal Li), charging at 0.2 V to a current value of 0.01 mA.
CC discharge: Discharge to 1.5 V at 0.2 mA. Table 1 shows the electrode bulk densities of Examples 1 to 4 and Comparative Examples 1 to 3 described above, the discharge capacity and charge / discharge efficiency in the first cycle, the discharge capacity after 50 cycles, and the average discharge voltage. As described above, unless the graphite particles, the organosilicon compound, and the carbon precursor are combined and the silicon content is not 40 to 80% by weight, the cycleability is not improved. In addition, the electrode bulk density is 1.5 to
Even when the pressure is increased to 1.6 g / cm 3 , it has a high discharge capacity and can maintain cycleability. However, if any one of the graphite particles, the organic silicon compound, and the carbon precursor is insufficient, or if the silicon content is not 40 to 80% by weight, problems occur in the electrode bulkiness, discharge capacity, and cycleability.
【００４３】[0043]
【表１】 [Table 1]
【００４４】実施例５、６、７ 実施例１〜４の他に黒鉛質量、炭素量と珪素含有量を変
えて充放電試験を行った。複合体作製条件、充放電試験
条件は実施例１と同様である。珪素含有量に対する放電
容量の関係を図１、黒鉛含有量に対する放電容量の関係
を図２、黒鉛含有量に対する平均放電電圧の関係を図３
に示す。Examples 5, 6, and 7 In addition to Examples 1 to 4, a charge / discharge test was conducted by changing the mass of graphite, the amount of carbon and the content of silicon. The conditions for preparing the composite and the conditions for the charge / discharge test are the same as in Example 1. FIG. 1 shows the relationship of the discharge capacity to the silicon content, FIG. 2 shows the relationship of the discharge capacity to the graphite content, and FIG. 3 shows the relationship of the average discharge voltage to the graphite content.
Shown in
【００４５】放電機構解析 図４に実施例１で用いた複合体の金属Ｌｉを対極として
充放電を行わせたときの放電におけるｄＸ／ｄＶ（Ｘ：
放電容量、Ｖ：放電電圧）を放電電圧Ｖに対してプロッ
トしたグラフを示す。ピークは放電電圧０．１Ｖと０．
３付近で得られた。また同様に図５〜７に炭素、ＳｉＯ
／黒鉛／炭素複合体、金属Ｓｉ／黒鉛／炭素複合体のグ
ラフをそれぞれ示す。炭素の場合、実施例１で見られた
放電電圧０．１Ｖ付近でピークを示した。しかし、Ｓｉ
Ｏ又は金属Ｓｉを含んだ黒鉛炭素複合体で見られた放電
電圧０．５Ｖ付近のピークは、実施例１のグラフでは観
察されなかった。Discharge Mechanism Analysis FIG. 4 shows dX / dV (X: X: dX) in discharge when charge / discharge was performed using metal Li of the composite used in Example 1 as a counter electrode.
4 is a graph in which discharge capacity (V: discharge voltage) is plotted against discharge voltage V. The peaks are 0.1V and 0.1V.
3 was obtained. Similarly, FIGS.
2 shows graphs of a graphite / graphite / carbon composite and a metal Si / graphite / carbon composite, respectively. In the case of carbon, it showed a peak near the discharge voltage of 0.1 V observed in Example 1. However, Si
The peak near the discharge voltage of 0.5 V observed in the graphite-carbon composite containing O or metal Si was not observed in the graph of Example 1.
【００４６】ＸＰＳ測定 実施例１の複合電極材料についてＸＰＳ分析を行った。
装置ならびに測定条件は、μ−ＸＰＳ（島津−Ｋｒａｔ
ｏｓ製 ＡＸＩＳ−１６５） Ａｌ−Ｋα ３０〜１５０
Ｗ（１５ｋＶ−２〜１０ｍＡ） ０．３×０．７ｍｍ 定
性スペクトルＰＥ＝１６０ｅＶ 定量スペクトルＰＥ＝
１０ｅｖ 検出角度：９０度である。このＸＰＳのＳｉ
２Ｐスペクトルを図８に示す。１０２．５〜１０７．５
（ｅＶ）付近に１つのピークを有している。XPS Measurement The composite electrode material of Example 1 was subjected to XPS analysis.
The apparatus and measurement conditions are as follows: μ-XPS (Shimadzu-Krat)
OS AXIS-165) Al-Kα 30 to 150
W (15 kV-2 to 10 mA) 0.3 × 0.7 mm Qualitative spectrum PE = 160 eV Quantitative spectrum PE =
10ev Detection angle: 90 degrees. This XPS Si
The 2P spectrum is shown in FIG. 102.5-107.5
It has one peak near (eV).
【００４７】[0047]
【発明の効果】本発明の複合電極材料は、これを電極成
形体に成形してリチウム二次電池用の電極として用いる
と、５００Ａｈ／ｋｇ以上の高い放電容量、真密度、タ
ップ密度などの特性が優れた電極となる。According to the composite electrode material of the present invention, when the composite electrode material is formed into a molded electrode and used as an electrode for a lithium secondary battery, characteristics such as a high discharge capacity of 500 Ah / kg or more, a true density, a tap density and the like are obtained. Is an excellent electrode.
【図１】珪素含有量に対する放電容量の関係を示すグラ
フ。FIG. 1 is a graph showing a relationship between a discharge capacity and a silicon content.
【図２】黒鉛含有量に対する放電容量の関係を示すグラ
フ。FIG. 2 is a graph showing a relationship between a graphite content and a discharge capacity.
【図３】黒鉛含有量に対する平均放電電圧の関係を示す
グラフ。FIG. 3 is a graph showing the relationship between the graphite content and the average discharge voltage.
【図４】実施例１で用いた複合体の金属Ｌｉを対極とし
て充放電を行わせたときの放電におけるｄＸ／ｄＶをＶ
に対してプロットしたグラフ。FIG. 4 is a graph showing that dX / dV in discharge when charging / discharging is performed using metal Li of the composite used in Example 1 as a counter electrode is V
Graph plotted against.
【図５】炭素の金属Ｌｉを対極として充放電を行わせた
ときの放電におけるｄＸ／ｄＶをＶに対してプロットし
たグラフ。FIG. 5 is a graph plotting dX / dV with respect to V in discharging when charging and discharging are performed using carbon metal Li as a counter electrode.
【図６】ＳｉＯ／黒鉛／炭素複合体の金属Ｌｉを対極と
して充放電を行わせたときの放電におけるｄＸ／ｄＶを
Ｖに対してプロットしたグラフ。FIG. 6 is a graph plotting dX / dV with respect to V in discharging when charging / discharging is performed using metal Li of the SiO / graphite / carbon composite as a counter electrode.
【図７】金属Ｓｉ／黒鉛／炭素複合体の金属Ｌｉを対極
として充放電を行わせたときの放電におけるｄＸ／ｄＶ
をＶに対してプロットしたグラフ。FIG. 7 shows dX / dV in discharge when charge / discharge is performed using metal Li of metal Si / graphite / carbon composite as a counter electrode.
Is a graph plotted against V.
【図８】実施例１で用いた複合体のＸＰＳのＳｉ２Ｐス
ペクトル。FIG. 8 is an XPS Si2P spectrum of the composite used in Example 1.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H029 AJ03 AJ05 AK03 AK05 AK16 AL06 AL07 AL08 AL11 AL12 AM02 AM03 AM04 AM06 AM07 CJ02 CJ08 CJ22 CJ28 DJ07 DJ18 HJ00 HJ01 HJ05 HJ07 HJ08 HJ18 HJ19 5H050 AA07 AA08 BA17 CA02 CA05 CA07 CA08 CA09 CA11 CA22 CB07 CB08 CB09 CB11 CB12 DA04 FA19 GA02 GA10 GA22 GA27 HA00 HA01 HA05 HA07 HA08 HA18 HA19 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 5H029 AJ03 AJ05 AK03 AK05 AK16 AL06 AL07 AL08 AL11 AL12 AM02 AM03 AM04 AM06 AM07 CJ02 CJ08 CJ22 CJ28 DJ07 DJ18 HJ00 HJ01 HJ05 HJ07 HJ08 HJ18 HJ19 CA05A07 CA08 CA11 CA22 CB07 CB08 CB09 CB11 CB12 DA04 FA19 GA02 GA10 GA22 GA27 HA00 HA01 HA05 HA07 HA08 HA18 HA19
Claims (8)
してなり、ＳｉＯ２換算での珪素含有量が４０〜８０重
量％であり、真密度が１．８×１０３ｋｇ／ｍ３以上、
タップ密度が０．８×１０３ｋｇ／ｍ３以上、比表面積
が８×１０３ｍ２／ｋｇ以下であることを特徴とする複
合電極材料。1. The composition contains graphite particles, amorphous carbon and silicon, has a silicon content of 40 to 80% by weight in terms of SiO 2 , and has a true density of 1.8 × 10 3 kg / m. 3 or more,
A composite electrode material having a tap density of 0.8 × 10 3 kg / m 3 or more and a specific surface area of 8 × 10 3 m 2 / kg or less.
１０２．５〜１０７．５（ｅＶ）付近に一つのピークを
有する請求項１記載の複合電極材料。2. In the Si2P spectrum of XPS,
The composite electrode material according to claim 1, which has one peak around 102.5 to 107.5 (eV).
とき、金属リチウムを対極として充放電を行わせたとき
の放電容量が５００Ａｈ／ｋｇ以上、平均放電電圧が
０．６Ｖ（対金属リチウム）以下である請求項１記載の
複合電極材料。3. When the content of graphite particles is 15 to 50% by weight, the discharge capacity is 500 Ah / kg or more and the average discharge voltage is 0.6 V (for metal) when charging / discharging is performed using metallic lithium as a counter electrode. 2. The composite electrode material according to claim 1, which is lithium or less.
せたときの放電において、ｄＸ／ｄＶ（Ｘ：放電容量、
Ｖ：放電電圧）を放電電圧Ｖに対してプロットしたグラ
フ中、０．５Ｖ付近にピークを有しない請求項１記載の
複合電極材料。4. In discharging when charging / discharging is performed using metallic lithium as a counter electrode, dX / dV (X: discharge capacity,
2. The composite electrode material according to claim 1, wherein the composite electrode material does not have a peak around 0.5 V in a graph in which (V: discharge voltage) is plotted against the discharge voltage V.
有機珪素化合物と炭素前駆体有機高分子化合物とを混合
し、非酸化性雰囲気中で加熱することを特徴とする複合
電極材料の製造方法。5. A method for producing a composite electrode material, comprising mixing graphite particles having an average particle diameter of 10 μm or less, an organosilicon compound and a carbon precursor organic polymer compound, and heating in a non-oxidizing atmosphere. .
を含む電極合材を成形してなり、電極合材のかさ密度が
１．２〜１．７×１０３ｋｇ／ｍ３であるリチウムイオ
ン二次電池用負極。6. An electrode mixture containing the composite electrode material according to claim 1, wherein the electrode mixture has a bulk density of 1.2 to 1.7 × 10 3 kg / m 3 . A negative electrode for a lithium ion secondary battery.
を含む電極合材を負極集電体に塗布してなり、電極合材
のかさ密度が１．２〜１．７×１０３ｋｇ／ｍ３である
リチウムイオン二次電池用負極。7. An electrode mixture comprising the composite electrode material according to claim 1 applied to a negative electrode current collector, wherein the electrode mixture has a bulk density of 1.2 to 1.7 × 10 3. kg / m 3 of a negative electrode for a lithium ion secondary battery.
ウムイオン二次電池。8. A lithium ion secondary battery using the negative electrode according to claim 6.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003048706A (en) * | 2001-08-02 | 2003-02-21 | Sumitomo Bakelite Co Ltd | Raw material for carbon material and carbon material obtained by using the same |
| JP2003089511A (en) * | 2001-09-12 | 2003-03-28 | Sumitomo Bakelite Co Ltd | Method for producing carbon material |
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