JPH0831419A - Negative electrode material for lithium secondary battery and lithium secondary battery - Google Patents
Negative electrode material for lithium secondary battery and lithium secondary batteryInfo
- Publication number
- JPH0831419A JPH0831419A JP6162417A JP16241794A JPH0831419A JP H0831419 A JPH0831419 A JP H0831419A JP 6162417 A JP6162417 A JP 6162417A JP 16241794 A JP16241794 A JP 16241794A JP H0831419 A JPH0831419 A JP H0831419A
- Authority
- JP
- Japan
- Prior art keywords
- mcmb
- negative electrode
- secondary battery
- lithium secondary
- brooks
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、エネルギー密度、放電
特性、サイクル特性などに優れたリチウム二次電池およ
びそれに用いる負極材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery excellent in energy density, discharge characteristics, cycle characteristics and the like, and a negative electrode material used therein.
【０００２】[0002]
【従来の技術】負極活物質としてリチウムを使用し、正
極活物質として金属カルコゲン化物あるいは金属酸化物
を使用し、電解液として非プロトン性有機溶媒に種々の
塩を溶解させた溶液を使用する、いわゆるリチウム二次
電池は、高エネルギー密度型二次電池として注目され、
広く研究されている。2. Description of the Related Art Lithium is used as a negative electrode active material, metal chalcogenide or metal oxide is used as a positive electrode active material, and a solution prepared by dissolving various salts in an aprotic organic solvent is used as an electrolytic solution. The so-called lithium secondary battery has attracted attention as a high energy density secondary battery,
Has been widely studied.
【０００３】従来のリチウム電池では、負極活物質とし
てのリチウムは、箔状の単体で用いられることが多く、
充放電を繰り返すことにより、樹枝状リチウムが析出し
て両極が短絡するという危険性を有している。In a conventional lithium battery, lithium as a negative electrode active material is often used in the form of a foil.
By repeating charging and discharging, there is a risk that dendritic lithium is deposited and both electrodes are short-circuited.
【０００４】樹枝状リチウムの析出を防止するために、
負極活物質として、リチウムとアルミニウム、鉛、カド
ミウムおよびインジウムというリチウムとの合金化が可
能な金属の少なくとも１種とを使用して、充電時にリチ
ウムを合金として析出させ、放電時にこの合金からリチ
ウムを溶解させる方法が提案されている（米国特許４０
０２４９２号）。しかしながら、このような方法によれ
ば、樹枝状リチウムの析出は抑止できるものの、エネル
ギー密度の減少およびサイクル寿命の低下という新たな
問題点が発生する。In order to prevent the deposition of dendritic lithium,
As the negative electrode active material, at least one kind of metal capable of alloying with lithium and lithium such as aluminum, lead, cadmium, and indium is used, lithium is deposited as an alloy during charging, and lithium is discharged from this alloy during discharging. A method of dissolving has been proposed (US Pat. No. 40).
02492). However, according to such a method, although the deposition of dendritic lithium can be suppressed, new problems such as a decrease in energy density and a decrease in cycle life occur.
【０００５】このような問題点を解決すべく、カーボン
材にリチウムを担持させることが試みられている。例え
ば、繊維状ないし粉末状のカーボン材にリチウムを担持
させることが提案されている（特開昭６３−１１４０５
６号公報、特開昭６２−２６８０５６号公報など）。し
かしながら、繊維状ないし粉末状のカーボン材を使用す
る場合には、電極の平滑性が得られない、炭素の結晶に
方向性があるため、導電性にも方向性が認められるなど
の問題点が生じる。In order to solve such problems, it has been attempted to support lithium on a carbon material. For example, it has been proposed to support lithium on a fibrous or powdery carbon material (Japanese Patent Laid-Open No. 63-11405).
No. 6, JP-A No. 62-268056, etc.). However, when a fibrous or powdery carbon material is used, there are problems that the smoothness of the electrode cannot be obtained, and the conductivity of carbon is directional because of the directional carbon crystal. Occurs.
【０００６】また、カーボン材としてＭＣＭＢ（メソカ
ーボンマイクロビーズ）を使用することも提案されてい
る（特公平４−１１５４５７号公報、特公平４−１１５
４５８号公報など）。It has also been proposed to use MCMB (mesocarbon microbeads) as a carbon material (Japanese Patent Publication No. 4-115457 and Japanese Patent Publication No. 4-115).
No. 458, etc.).
【０００７】ＭＣＭＢの構造には、ブルックス−テーラ
ー型、ホンダ型、ヒュッティンガー型、コバック−ルイ
ス型などがあり、これらは、種々の特性上相互に明確に
相違している。The structure of MCMB includes Brooks-Taylor type, Honda type, Huttinger type, Kovac-Lewis type and the like, which are clearly different from each other due to various characteristics.
【０００８】即ち、G.H.Taylorらは、コールタールピッ
チのキノリン可溶分を熱処理した際に得られるＭＣＭＢ
を偏光顕微鏡と制限視野電子線回折により観察した結
果、図１に示す様に、このＭＣＭＢは、縮合多環芳香族
化合物の平面分子が一定方向に薄層（ラメラ）を形成
し、この薄層が積層したものであることを報告した（Ca
rbon,8,185（1965））。この構造を有するＭＣＭＢは、
ブルックス−テーラー型ＭＣＭＢと呼ばれている。この
ＭＣＭＢを偏光顕微鏡で観察すると、光軸を含む面で
は、アイソジャー（十字架）によって区分けされる領域
の色は、第１および第３象限が青色となり、第２および
第４象限が黄色となる。[0008] That is, GH Taylor et al. Obtained MCMB obtained by heat-treating a quinoline soluble component of coal tar pitch.
As a result of observing with a polarizing microscope and a selected area electron beam diffraction, as shown in FIG. 1, in this MCMB, planar molecules of the condensed polycyclic aromatic compound form a thin layer (lamella) in a certain direction, and this thin layer It was reported that they were laminated (Ca
rbon, 8,185 (1965)). MCMB with this structure
It is called Brooks-Taylor type MCMB. When observing this MCMB with a polarization microscope, in the plane including the optical axis, the color of the region divided by the isogen (cross) is blue in the first and third quadrants and yellow in the second and fourth quadrants. .
【０００９】また、本田らは、コールタールピッチのキ
ノリン可溶分に特定のカーボンブラックを添加したもの
を熱処理した際に得られるＭＣＭＢにおいては、ブルッ
クス−テーラー型とは異なり、図２に示す様に、光軸を
含む面では、分子はその長軸が光軸にほぼ垂直になる様
に配向し、光軸に垂直な面では、同心円状に配向してい
ることを報告した（炭素、７３、５１（１９７３））。
この構造を有するＭＣＭＢは、ホンダ型ＭＣＭＢと呼ば
れている。このＭＣＭＢを偏光顕微鏡で観察すると、光
軸を含む面では、アイソジャー（十字架）によって区分
けされる領域の色は、第１および第３象限が黄色とな
り、第２および第４象限が青色となる。In addition, Honda et al., In MCMB obtained by heat-treating coal tar pitch having quinoline-soluble component added with specific carbon black, unlike Brooks-Taylor type, as shown in FIG. In the plane containing the optical axis, it was reported that the molecules are oriented so that their long axes are almost perpendicular to the optical axis, and in the plane perpendicular to the optical axis, they are concentrically oriented (carbon, 73 , 51 (1973)).
An MCMB having this structure is called a Honda MCMB. When observing this MCMB with a polarization microscope, in the plane including the optical axis, the colors of the regions divided by the isogers (crosses) are yellow in the first and third quadrants and blue in the second and fourth quadrants. .
【００１０】しかしながら、上記の公報では、用いられ
るＭＣＭＢの構造と電極特性との対応関係が明確にされ
ていないので、どの様な構造のＭＣＭＢを使用する場合
にどの様な効果が達成されるかは、全く不明である。However, in the above publication, since the correspondence between the structure of the MCMB used and the electrode characteristics is not clarified, what kind of effect is achieved when using the MCMB having any structure. Is completely unknown.
【００１１】[0011]
【発明が解決しようとする課題】したがって、本発明
は、カーボン材を負極物質として使用するリチウム二次
電池用の新たなＭＣＭＢ系負極材料を提供することを主
な目的とする。Therefore, the main object of the present invention is to provide a new MCMB-based negative electrode material for a lithium secondary battery using a carbon material as a negative electrode material.
【００１２】さらに、本発明は、上記の新たなＭＣＭＢ
系負極材料を使用するリチウム二次電池を提供すること
をも目的とする。Furthermore, the present invention provides the above-mentioned new MCMB.
It is also an object to provide a lithium secondary battery using a system negative electrode material.
【００１３】[0013]
【課題を解決するための手段】本発明者は、上記のよう
な技術の現状に鑑みて鋭意研究を重ねる間に、ＭＣＭＢ
の構造によって電極特性が異なること、およびブルック
ス−テーラー型構造のＭＣＭＢが負極材料として特に優
れた性能を発揮することを見出した。Means for Solving the Problems The present inventor has conducted an earnest research in view of the current state of the art as described above, and
It was found that the electrode characteristics differ depending on the structure of No. 3, and that the MCMB of Brooks-Taylor structure exhibits particularly excellent performance as a negative electrode material.
【００１４】本発明はこのような新規な知見に基いて完
成されたものである。The present invention has been completed based on such novel knowledge.
【００１５】即ち、本発明は、下記のリチウム二次電池
用負極材料およびこれを使用するリチウム二次電池を提
供するものである。That is, the present invention provides the following negative electrode material for a lithium secondary battery and a lithium secondary battery using the same.
【００１６】１．ブルックステーラー型メソフェーズ小
球体を焼成処理することにより得られ、真比重が１．５
０〜２．００である炭化ブルックス−テーラー型メソフ
ェーズ小球体からなるリチウム二次電池用負極材料。1. The true specific gravity is 1.5, which is obtained by firing a Brook-Stellar type mesophase sphere.
A negative electrode material for lithium secondary batteries comprising Brooks-Taylor type mesophase spherules having a carbon number of 0 to 2.00.
【００１７】２．上記項１に記載のリチウム二次電池用
負極材料を負極の構成材料とするリチウム二次電池。2. A lithium secondary battery comprising the negative electrode material for a lithium secondary battery according to item 1 as a constituent material of a negative electrode.
【００１８】３．ブルックル−テーラー型メソフェーズ
小球体を焼成処理することにより得られ、真比重が２．
００〜２．２１である黒鉛化ブルックス−テーラー型メ
ソフェーズ小球体からなるリチウム二次電池用負極材
料。3. A true specific gravity of 2. was obtained by firing a Brookle-Taylor type mesophase microsphere.
A negative electrode material for a lithium secondary battery comprising graphitized Brooks-Taylor type mesophase spherules having a size of 00 to 2.21.
【００１９】４．上記項２に記載のリチウム二次電池用
負極材料を負極の構成材料とするリチウム二次電池。4. A lithium secondary battery comprising the negative electrode material for a lithium secondary battery according to item 2 as a constituent material of a negative electrode.
【００２０】本発明において使用する負極材料となるＭ
ＣＭＢ（生品）の原料は、常法に従って、コールタール
やピッチから製造される。このようなＭＣＭＢは、特に
限定されるものではないが、例えば、特開昭５８−１６
１０４９号公報、特開昭６３−７０９４９号公報などに
開示されている方法により製造される。M as the negative electrode material used in the present invention
The raw material of CMB (raw product) is produced from coal tar or pitch according to a conventional method. Such MCMB is not particularly limited, but for example, JP-A-58-16 is used.
It is manufactured by the method disclosed in Japanese Patent No. 1049, Japanese Patent Laid-Open No. 63-70949 and the like.
【００２１】ＭＣＭＢ（生品）の炭化焼成は、窒素雰囲
気、アルゴン雰囲気などの非酸化性雰囲気中もしくは真
空脱気などの減圧下６００〜１５００℃程度の温度で１
〜５時間程度の条件下に行なう。Carbonization firing of MCMB (raw product) is performed at a temperature of about 600 to 1500 ° C. in a non-oxidizing atmosphere such as a nitrogen atmosphere or an argon atmosphere or under reduced pressure such as vacuum deaeration.
Perform under conditions of about 5 hours.
【００２２】また、ＭＣＭＢ（生品）の黒鉛化焼成は、
窒素雰囲気、アルゴン雰囲気などの非酸化性雰囲気中２
５００〜３０００℃程度の温度で１〜５時間程度の条件
下に行なう。Further, the graphitization firing of MCMB (raw product) is
In a non-oxidizing atmosphere such as a nitrogen atmosphere or an argon atmosphere 2
It is performed at a temperature of about 500 to 3000 ° C. for about 1 to 5 hours.
【００２３】ブルックス−テーラー型ＭＣＭＢの炭化品
を使用する場合には、電解液として１モル／ｌの濃度で
ＬｉＣｌＯ4 を溶解させたプロピレンカーボネートを用
い、電流密度を０．１ｍＡ／ｃｍ2 とする条件下に、リ
チウム二次電池の放電容量は３６０Ａｈ／ｋｇ程度、充
放電効率は８５％以上となる。When a Brooks-Taylor type MCMB carbonized product is used, propylene carbonate in which LiClO 4 is dissolved at a concentration of 1 mol / l is used as the electrolytic solution, and the current density is 0.1 mA / cm 2 . Under the conditions, the discharge capacity of the lithium secondary battery is about 360 Ah / kg, and the charge / discharge efficiency is 85% or more.
【００２４】ブルックス−テーラー型ＭＣＭＢの黒鉛炭
化品を使用する場合には、電解液として１モル／ｌの濃
度でＬｉＣｌＯ4 を溶解させたエチレンカーボネートと
ジエチルカーボネート（体積比で１：１）の混合溶媒を
用い、電流密度を０．１ｍＡ／ｃｍ2 とする条件下に、
リチウム二次電池の放電容量は３５０Ａｈ／ｋｇ程度、
充放電効率は８５％以上となる。When a Brooks-Taylor type MCMB graphite carbonized product is used, a mixture of ethylene carbonate and diethyl carbonate (1: 1 by volume) in which LiClO 4 is dissolved at a concentration of 1 mol / l is used as an electrolytic solution. Using a solvent and a current density of 0.1 mA / cm 2 ,
The discharge capacity of the lithium secondary battery is about 350 Ah / kg,
The charge / discharge efficiency is 85% or more.
【００２５】ブルックス−テーラー型ＭＣＭＢが、ホン
ダ型ＭＣＭＢなどの他の構造を有するＭＣＭＢに比し
て、リチウム二次電池負極材料として優れた特性を発揮
する理由は、未だ解明されていないが、以下のように推
測される。The reason why the Brooks-Taylor type MCMB exhibits excellent characteristics as a lithium secondary battery negative electrode material as compared with MCMB having other structures such as Honda type MCMB has not yet been elucidated. Is speculated as.
【００２６】ブルックス−テーラー型ＭＣＭＢの球体
は、図１に示す様に、縮合多環芳香族分子が光軸方向に
垂直に積層した構造をしている。したがって、ＭＣＭＢ
の球体表面に対して炭素の端面（エッジ面）が垂直に配
向しているため、充放電に際し、リチウムイオンが出入
りしやすく、その拡散速度が速いものと考えられる。As shown in FIG. 1, the Brooks-Taylor type MCMB sphere has a structure in which condensed polycyclic aromatic molecules are laminated perpendicularly to the optical axis direction. Therefore, MCMB
It is considered that since the carbon end faces (edge faces) are oriented perpendicularly to the sphere surface, the lithium ions easily enter and leave during charge and discharge, and the diffusion speed thereof is fast.
【００２７】これに対し、ホンダ型ＭＣＭＢの球体で
は、図２に示す様に、光軸を含む面では、縮合多環芳香
族分子の長軸が光軸にほぼ平行になるように配向し、光
軸に垂直な面では、同心円状に配向している。したがっ
て、ＭＣＭＢの球体表面に対して炭素の端面（エッジ
面）が平行に配向しているため、充放電に際し、リチウ
ムイオンが出入りしにくく、その拡散速度が遅いものと
考えられる。On the other hand, in the sphere of Honda MCMB, as shown in FIG. 2, in the plane including the optical axis, the fused polycyclic aromatic molecule is oriented so that the long axis thereof is substantially parallel to the optical axis, The plane perpendicular to the optical axis is concentrically oriented. Therefore, since the carbon end faces (edge faces) are oriented parallel to the surface of the spheres of MCMB, it is considered that lithium ions are hard to come in and out during charge and discharge, and the diffusion speed thereof is slow.
【００２８】本発明によるリチウム二次電池用負極は、
公知の正極、電解液、電解質などと組み合わせて、常法
により、二次電池を構成することが出来る。The negative electrode for a lithium secondary battery according to the present invention comprises:
A secondary battery can be formed by a conventional method in combination with a known positive electrode, electrolytic solution, electrolyte and the like.
【００２９】正極物質としては、特に限定されず、金属
カルコゲン化物、金属酸化物、導電性を有する共役系高
分子物質などを用いることが出来る。The positive electrode material is not particularly limited, and a metal chalcogenide, a metal oxide, a conjugated polymer material having conductivity, or the like can be used.
【００３０】本発明によるＭＣＭＢ炭化品を負極材料と
する場合の電解液としては、プロピレンカーボネート系
の非プロトン性溶媒にリチウム塩を溶解させたものを用
いることが出来る。When the MCMB carbonized product according to the present invention is used as a negative electrode material, an electrolyte prepared by dissolving a lithium salt in a propylene carbonate-based aprotic solvent can be used.
【００３１】本発明によるＭＣＭＢ黒鉛化品を負極材料
とする場合の電解液としては、エチレンカーボネート系
の非プロトン性溶媒にリチウム塩を溶解させたものを用
いることが出来る。エチレンカーボネートは、粘度が高
いため、常法に従って通常ジエチルカーボネート、ジエ
チルエーテル、テトラヒドロフラン、２−メチルテトラ
ヒドロフラン、１，２−ジメトキシエタン、アセトニト
リルなどの低粘度溶媒を混合して使用する。When the MCMB graphitized product according to the present invention is used as a negative electrode material, an electrolyte prepared by dissolving a lithium salt in an ethylene carbonate aprotic solvent can be used. Since ethylene carbonate has a high viscosity, a low-viscosity solvent such as diethyl carbonate, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane or acetonitrile is usually mixed and used according to a conventional method.
【００３２】また、電解質としてのリチウム塩は、Ｌｉ
ＰＦ6 、ＬｉＣｌＯ4 、ＬｉＢＦ4、ＬｉＡｓＦ6 、Ｌ
ｉＳｂＦ6 などの溶媒和しにくいアニオンを生成する塩
が用いられる。The lithium salt used as the electrolyte is Li
PF 6 , LiClO 4 , LiBF 4 , LiAsF 6 , L
A salt that produces an anion that is difficult to solvate, such as iSbF 6, is used.
【００３３】本発明によるリチウム二次電池は、通常使
用される多孔質ポリプロピレン製不織布などのポリオレ
フィン系の多孔質膜のセパレータ、集電体、ガスケッ
ト、封口板、ケースなどの公知の電池構成要素と前記の
本発明によるカーボン負極を使用し、常法に従って、円
筒型、角型あるいはボタン型などの任意の形態に組み立
てることが出来る。The lithium secondary battery according to the present invention has well-known battery components such as a separator of a porous polyolefin film such as a porous polypropylene non-woven fabric which is usually used, a current collector, a gasket, a sealing plate and a case. Using the carbon negative electrode according to the present invention, it can be assembled into any shape such as a cylindrical shape, a square shape or a button shape according to a conventional method.
【００３４】[0034]
【実施例】以下に実施例および比較例を示し、本発明の
特徴とするところをより一層明確にする。EXAMPLES Examples and comparative examples will be shown below to further clarify the features of the present invention.
【００３５】なお、偏光顕微鏡観察に際しては、ＭＣＭ
Ｂと樹脂とを混合して成型し、研磨を行い、光源にハロ
ゲン白熱灯を用いたＺｅｉｓｓ社製オルソルックス反射
偏光顕微鏡により、直交ニコル下で石膏検板を入れて組
織を観察した。When observing with a polarization microscope, MCM
B and a resin were mixed, molded, and polished, and a gypsum test plate was put under a crossed Nicols by a Zeiss Orsolux reflection polarization microscope using a halogen incandescent lamp as a light source, and the structure was observed.
【００３６】実施例１ Ｉ．ブルックステーラー型ＭＣＭＢの調製 出発原料として一次ＱＩを除去したコールタールピッチ
を３ｋｇ／ｃｍ2 ・Ｇの加圧下、４００℃で８時間反応
させ、生成したＭＣＭＢを高温遠心分離機により反応タ
ールから分離し、トルエンで洗浄した後、窒素雰囲気下
で減圧乾燥を行った。Example 1 I. Preparation of Brooks Taylor type MCMB Coal tar pitch from which primary QI was removed was reacted as a starting material under a pressure of 3 kg / cm 2 · G for 8 hours at 400 ° C., and the produced MCMB was separated from the reaction tar by a high temperature centrifuge. After washing with toluene, it was dried under reduced pressure in a nitrogen atmosphere.
【００３７】得られたＭＣＭＢ生品の構造を偏光顕微鏡
で観察したところ、球体の光軸を含む面では、アイソジ
ャーによって区分される領域の色は、第１および第３象
限が青色、第２および４象限が黄色であることから、こ
のＭＣＭＢは、ブルックス−テーラー型構造を有するこ
とが確認された。When the structure of the obtained MCMB raw product was observed with a polarizing microscope, in the plane including the optical axis of the sphere, the colors of the regions divided by the isogens were blue in the first and third quadrants and second in the second quadrant. It was confirmed that the MCMB had a Brooks-Taylor type structure because of the yellow color in the four quadrants.
【００３８】ＩＩ．ブルックステーラー型ＭＣＭＢの炭
化焼成処理 得られたＭＣＭＢを窒素雰囲気中１０００℃で１時間焼
成し、炭化した。得られたＭＣＭＢ炭化品の構造を偏光
顕微鏡で観察したところ、ブルックス−テーラー型であ
った。II. Carbonization and calcination treatment of Brook Stellar type MCMB The obtained MCMB was calcinated and calcined at 1000 ° C. for 1 hour in a nitrogen atmosphere. When the structure of the obtained MCMB carbonized product was observed with a polarizing microscope, it was Brooks-Taylor type.
【００３９】ＩＩＩ．負極体の作成 上記で得られたＭＣＭＢ炭化品９５重量部とデイスパー
ジョンタイプのＰＴＦＥ（ダイキン工業（株）製、Ｄ−
１）５重量部とを混合し、液相で均一に攪拌した後、乾
燥させ、ペースト状とした。このペースト状負極用物質
３０ｍｇをプレス機により成型し、直径１０ｍｍの負極
体を作成した後、得られた負極体を２００℃で６時間真
空乾燥させた。III. Preparation of Negative Electrode Body 95 parts by weight of MCMB carbonized product obtained above and dispersion type PTFE (manufactured by Daikin Industries, Ltd., D-
1) 5 parts by weight were mixed, stirred uniformly in the liquid phase, and then dried to obtain a paste. 30 mg of this paste-like negative electrode substance was molded by a press to form a negative electrode body having a diameter of 10 mm, and the obtained negative electrode body was vacuum dried at 200 ° C. for 6 hours.
【００４０】ＩＶ．電池の作成 上記で得られた負極体としてのＭＣＭＢ炭化品、正極体
としてのＬｉＣｏＯ2および電解液として１モル／ｌの
濃度にＬｉＣｌＯ4 を溶解させたプロピレンカーボネー
トを用い、セパレータとしてポリプロピレン不織布を用
いて、リチウム二次電池を作成した。その断面図を図３
に示す。図３において、１は正極体、２はセパレータ、
３は負極体、４はケース、５は封口板、６は絶縁パッキ
ングをそれぞれ示す。IV. Preparation of Battery Using MCMB carbonized product as the negative electrode body obtained above, LiCoO 2 as the positive electrode body, and propylene carbonate in which LiClO 4 was dissolved at a concentration of 1 mol / l as the electrolytic solution, and using polypropylene nonwoven fabric as the separator. , A lithium secondary battery was created. Its sectional view is shown in FIG.
Shown in In FIG. 3, 1 is a positive electrode body, 2 is a separator,
Reference numeral 3 is a negative electrode, 4 is a case, 5 is a sealing plate, and 6 is an insulating packing.
【００４１】Ｖ．電池特性の測定 上記で得られたリチウム二次電池の放電特性を測定し
た。V. Measurement of Battery Characteristics The discharge characteristics of the lithium secondary battery obtained above were measured.
【００４２】測定は、０．１ｍＡ／ｃｍ2 の定電流充放
電下で行い、放電容量は、電池電圧が２．０Ｖに低下す
るまでの容量とした。結果を表１に示す。The measurement was performed under a constant current charge / discharge of 0.1 mA / cm 2 , and the discharge capacity was the capacity until the battery voltage dropped to 2.0V. The results are shown in Table 1.
【００４３】実施例２ Ｉ．ブルックステーラー型ＭＣＭＢの黒鉛化焼成処理 実施例１と同様にして調製したブルックステーラー型Ｍ
ＣＭＢ生品を２８００℃で１時間焼成し、黒鉛化した。
得られたＭＣＭＢ黒鉛化品の構造を偏光顕微鏡で観察し
たところ、ブルックス−テーラー型であった。Example 2 I. Graphitization and firing treatment of Brooks Taylor type MCMB Brooks Taylor type M prepared in the same manner as in Example 1.
The CMB raw product was fired at 2800 ° C. for 1 hour to be graphitized.
When the structure of the obtained MCMB graphitized product was observed with a polarizing microscope, it was Brooks-Taylor type.
【００４４】ＩＩ．負極体の作成 上記で焼成処理を行った黒鉛化ＭＣＭＢを用いて、実施
例１と同様にして負極体を作成した。II. Preparation of Negative Electrode Body A negative electrode body was prepared in the same manner as in Example 1 by using the graphitized MCMB subjected to the above-mentioned firing treatment.
【００４５】ＩＩＩ．電池の作成 電解液として１モル／ｌの濃度にＬｉＣｌＯ4 を溶解さ
せたエチレンカーボネートとジエチルカーボネートの混
合溶媒（体積比で１：１）を用いる以外は、実施例１と
同様にしてリチウム二次電池を作成した。III. Preparation of Battery Secondary lithium secondary battery was prepared in the same manner as in Example 1 except that a mixed solvent of ethylene carbonate and diethyl carbonate (1: 1 by volume) in which LiClO 4 was dissolved at a concentration of 1 mol / l was used as an electrolytic solution. I made a battery.
【００４６】ＩＶ．電池特性の測定 得られたリチウム二次電池の放電特性を実施例１と同様
に測定した。結果を表１に示す。IV. Measurement of Battery Characteristics The discharge characteristics of the obtained lithium secondary battery were measured in the same manner as in Example 1. The results are shown in Table 1.
【００４７】比較例１ 出発原料として一次ＱＩを除去したコールタールピッチ
にファーネスブラックを３重量％添加したものを原料と
し、３ｋｇ／ｃｍ2 ・Ｇの加圧下４００℃で８時間反応
を行い、生成したＭＣＭＢを高温遠心分離機により反応
ピッチから分離した。この際、ファーネスブラックは、
ピッチマトリックス側に分離された。得られたＭＣＭＢ
をトルエンで洗浄後、窒素雰囲気下で減圧乾燥を行っ
た。得られたＭＣＭＢ生品の構造を偏光顕微鏡で観察し
たところ、球体の光軸を含む面では、アイソジャーによ
って区分される領域の色は、第１および第３象眼が黄
色、第２および第４象眼が青色であることから、このＭ
ＣＭＢはホンダ型構造を有していることがわかった。Comparative Example 1 As a starting material, a coal tar pitch from which primary QI was removed and 3% by weight of furnace black was added was used as a starting material, and the reaction was carried out at 400 ° C. for 8 hours under a pressure of 3 kg / cm 2 · G to produce a product. The prepared MCMB was separated from the reaction pitch by a high temperature centrifuge. At this time, Furnace Black
Separated on the pitch matrix side. The obtained MCMB
After washing with toluene, it was dried under reduced pressure in a nitrogen atmosphere. When the structure of the obtained MCMB raw product was observed with a polarization microscope, in the plane including the optical axis of the sphere, the colors of the regions divided by the Isogen were yellow in the first and third inlays, and second and fourth. Since the inlay is blue, this M
It was found that the CMB has a Honda structure.
【００４８】得られたＭＣＭＢを窒素雰囲気中１０００
℃で１時間焼成し、炭化した。得られたＭＣＭＢ炭化品
の構造を偏光顕微鏡で観察したところ、ホンダ型であっ
た。The obtained MCMB was treated with 1000 in a nitrogen atmosphere.
Carbonization was performed by firing at 1 ° C for 1 hour. When the structure of the obtained MCMB carbonized product was observed with a polarizing microscope, it was found to be a Honda type.
【００４９】次いで、実施例１と同様にして、負極体の
作成および電池の作成を行い、電極特性の測定を行っ
た。結果を表１に示す。Then, in the same manner as in Example 1, a negative electrode body and a battery were prepared and the electrode characteristics were measured. The results are shown in Table 1.
【００５０】比較例２ 比較例１と同様にして調整したホンダ型ＭＣＭＢ生品を
２８００℃で１時間焼成し、黒鉛化した。得られたＭＣ
ＭＢ黒鉛化品の構造を偏光顕微鏡で観察したところ、ホ
ンダ型であった。Comparative Example 2 A Honda type MCMB raw material prepared in the same manner as in Comparative Example 1 was fired at 2800 ° C. for 1 hour to be graphitized. The obtained MC
When the structure of the MB graphitized product was observed with a polarizing microscope, it was a Honda type.
【００５１】次いで、実施例１と同様にして、負極体の
作成および電池の作成を行い、電極特性の測定を行っ
た。結果を表１に示す。Then, in the same manner as in Example 1, a negative electrode body and a battery were prepared, and the electrode characteristics were measured. The results are shown in Table 1.
【００５２】[0052]
【表１】 [Table 1]
【００５３】表１から明らかな様に、ブルックス−テー
ラー型ＭＣＭＢの炭化品または黒鉛化品を負極材料とし
て使用する場合には、ホンダ型ＭＣＭＢの炭化品または
黒鉛化品を負極材料として使用する場合よりも、リチウ
ム二次電池の放電容量および充放電効率が著しく改善さ
れることが判明した。As is clear from Table 1, when a carbonized product or graphitized product of Brooks-Taylor type MCMB is used as a negative electrode material, a carbonized product or graphitized product of Honda type MCMB is used as a negative electrode material. It was found that the discharge capacity and charging / discharging efficiency of the lithium secondary battery are significantly improved.
【００５４】[0054]
【発明の効果】本発明によれば、ＭＣＭＢの炭化品或い
は黒鉛化品をリチウム二次電池の負極材料として使用す
る場合に、ＭＣＭＢ生品の構造を予め偏光顕微鏡により
調べておくことにより、これを使用する二次電池の電極
特性を予測することができる。According to the present invention, when a carbonized product or a graphitized product of MCMB is used as a negative electrode material of a lithium secondary battery, the structure of the MCMB raw product is examined in advance by a polarization microscope. It is possible to predict the electrode characteristics of the secondary battery using
【００５５】その結果、電池作成の前段階でＭＣＭＢの
出発原料であるコールタールを適切に選択し、あるいは
コールタールを適切に処理することにより、所望のＭＣ
ＭＢを得て、高充放電効率のリチウム二次電池用の負極
およびリチウム二次電池を構成することができる。As a result, the desired MC was obtained by appropriately selecting the coal tar as the starting material of MCMB or appropriately treating the coal tar in the pre-stage of battery production.
By obtaining MB, a negative electrode for a lithium secondary battery with high charge / discharge efficiency and a lithium secondary battery can be constructed.
【図１】ブルックス−テーラー型ＭＣＭＢの構造を示す
概念図である。FIG. 1 is a conceptual diagram showing the structure of a Brooks-Taylor type MCMB.
【図２】ホンダ型ＭＣＭＢの構造を示す概念図である。FIG. 2 is a conceptual diagram showing the structure of a Honda MCMB.
【図３】実施例で作成したリチウム二次電池の断面図で
ある。FIG. 3 is a cross-sectional view of a lithium secondary battery created in an example.
１：負極 ２：セパレータ ３：正極 ４：ケース ５：封口板 ６：絶縁パッキング 1: Negative electrode 2: Separator 3: Positive electrode 4: Case 5: Sealing plate 6: Insulating packing
Claims (4)
体を焼成処理することにより得られ、真比重が１．５０
〜２．００である炭化ブルックス−テーラー型メソフェ
ーズ小球体からなるリチウム二次電池用負極材料。1. A true specific gravity of 1.50 obtained by firing a Brooks-Taylor type mesophase small sphere.
A negative electrode material for lithium secondary batteries comprising Brooks-Taylor type mesophase spherules having a size of about 2.00.
材料を負極の構成要素とするリチウム二次電池。2. A lithium secondary battery comprising the negative electrode material for a lithium secondary battery according to claim 1 as a constituent of a negative electrode.
体を焼成処理することにより得られ、真比重が２．００
〜２．２１である黒鉛化ブルックス−テーラー型メソフ
ェーズ小球体からなるリチウム二次電池用負極材料。3. A true specific gravity obtained by calcining Brooks-Taylor type mesophase spherules and having a true specific gravity of 2.00.
A negative electrode material for lithium secondary batteries, which comprises graphitized Brooks-Taylor type mesophase spherules of .about.2.21.
材料を負極の構成要素とするリチウム二次電池。4. A lithium secondary battery comprising the negative electrode material for a lithium secondary battery according to claim 3 as a component of a negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6162417A JPH0831419A (en) | 1994-07-14 | 1994-07-14 | Negative electrode material for lithium secondary battery and lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6162417A JPH0831419A (en) | 1994-07-14 | 1994-07-14 | Negative electrode material for lithium secondary battery and lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0831419A true JPH0831419A (en) | 1996-02-02 |
Family
ID=15754208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6162417A Pending JPH0831419A (en) | 1994-07-14 | 1994-07-14 | Negative electrode material for lithium secondary battery and lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0831419A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6852449B2 (en) | 2002-08-29 | 2005-02-08 | Quallion Llc | Negative electrode including a carbonaceous material for a nonaqueous battery |
| US6998192B1 (en) | 2002-08-29 | 2006-02-14 | Quallion Llc | Negative electrode for a nonaqueous battery |
| US7174207B2 (en) | 2004-09-23 | 2007-02-06 | Quallion Llc | Implantable defibrillator having reduced battery volume |
| KR100749416B1 (en) * | 1999-12-08 | 2007-08-14 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
| JP2011184293A (en) * | 2009-10-22 | 2011-09-22 | Showa Denko Kk | Graphite material, carbonaceous material for battery electrode, and battery |
| KR20190077571A (en) | 2016-11-18 | 2019-07-03 | 에어 워터 가부시키가이샤 | Method for manufacturing compound semiconductor substrate and compound semiconductor substrate |
-
1994
- 1994-07-14 JP JP6162417A patent/JPH0831419A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100749416B1 (en) * | 1999-12-08 | 2007-08-14 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery and method of preparing same |
| US6852449B2 (en) | 2002-08-29 | 2005-02-08 | Quallion Llc | Negative electrode including a carbonaceous material for a nonaqueous battery |
| US6998192B1 (en) | 2002-08-29 | 2006-02-14 | Quallion Llc | Negative electrode for a nonaqueous battery |
| US7174207B2 (en) | 2004-09-23 | 2007-02-06 | Quallion Llc | Implantable defibrillator having reduced battery volume |
| JP2011184293A (en) * | 2009-10-22 | 2011-09-22 | Showa Denko Kk | Graphite material, carbonaceous material for battery electrode, and battery |
| KR20190077571A (en) | 2016-11-18 | 2019-07-03 | 에어 워터 가부시키가이샤 | Method for manufacturing compound semiconductor substrate and compound semiconductor substrate |
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