JPH065288A - Carbon electrode and lithium secondary battery using same electrode - Google Patents
Carbon electrode and lithium secondary battery using same electrodeInfo
- Publication number
- JPH065288A JPH065288A JP4184556A JP18455692A JPH065288A JP H065288 A JPH065288 A JP H065288A JP 4184556 A JP4184556 A JP 4184556A JP 18455692 A JP18455692 A JP 18455692A JP H065288 A JPH065288 A JP H065288A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- secondary battery
- lithium secondary
- carbonaceous material
- carbon
- 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.)
- Granted
Links
Classifications
-
- 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]
【産業上の利用分野】この発明は、カ―ボン電極とこれ
を用いたリチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon electrode and a lithium secondary battery using the same.
【０００２】[0002]
【従来の技術】エチレンカ―ボネ―トなどの有機溶媒に
ＬｉＣＦ3 ＳＯ3 などのリチウム塩を溶解させて有機電
解液としたリチウム二次電池において、負極にリチウム
またはリチウム合金を用いたものでは、内部短絡を起こ
しやすく、電池特性の劣化や安全性の面で問題があつ
た。BACKGROUND ART Echirenka - BONNET - in a lithium secondary battery in which an organic solvent by dissolving a lithium salt such as LiCF 3 SO 3 in the organic electrolyte solution, such bets, those using lithium or a lithium alloy for the negative electrode, It is easy to cause an internal short circuit, and there were problems in terms of deterioration of battery characteristics and safety.
【０００３】このため、リチウムまたはリチウム合金に
代えて、活性炭、黒鉛などの炭素質を負極担持体として
用いることが、特開昭５７−２０８０７９号公報、特開
昭５８−３５８８１号公報、特開昭５９−１４３２８０
号公報、「Ｊｏｕｒｎａｌｏｆ Ｅｌｅｃｔｒｏｃｈｅ
ｍｉｃａｌ Ｓｏｃｉｅｔｙ」第２２２頁（１９７０
年）、「第２９回電池討論会講演要旨集」第１３９頁
（１９８８年）などで、検討されている。Therefore, instead of lithium or a lithium alloy, carbonaceous materials such as activated carbon and graphite may be used as a negative electrode carrier, as disclosed in JP-A-57-208079 and JP-A-58-35881. Sho 59-143280
Publication, "Journalof Electroche
medical Society ", page 222 (1970)
), "Abstracts of the 29th Battery Symposium", page 139 (1988), etc.
【０００４】また、特開昭６２−１２２０６６号公報に
は、水素／炭素の原子比が０．１５未満であり、Ｘ線広
角回析より求めた（００２）面の面間隔が３．３７Å以
上、ｃ軸方向の結晶子の大きさが１５０Å以下の黒鉛類
似構造を有する炭素質を、非水溶媒電池の負極担持体と
して用いることが、提案されている。In Japanese Patent Laid-Open No. 62-122066, the atomic ratio of hydrogen / carbon is less than 0.15, and the (002) plane spacing determined by X-ray wide angle diffraction is 3.37 Å or more. It has been proposed to use a carbonaceous material having a graphite-like structure having a crystallite size in the c-axis direction of 150 Å or less as a negative electrode carrier of a non-aqueous solvent battery.
【０００５】このような炭素質を担持体としてリチウム
を活物質とした負極を用いると、リチウムまたはリチウ
ム合金の板状物を負極とした電池に比べ、体積エネルギ
―密度はある程度犠牲になるが、充放電の可逆性や安全
性は飛躍的に向上する。また、前記の黒鉛類似構造を有
する炭素質の使用は、自己放電の抑制とサイクル特性の
向上にも好結果を与えることが知られている。When a negative electrode having such a carbonaceous material as a carrier and lithium as an active material is used, the volume energy density is sacrificed to some extent as compared with a battery having a negative electrode made of a plate of lithium or a lithium alloy. The reversibility and safety of charge and discharge are dramatically improved. Further, it is known that the use of the carbonaceous material having the above graphite-like structure gives good results in suppressing self-discharge and improving cycle characteristics.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
如き炭素質材料を負極担持体として使用したリチウム二
次電池においては、分極が大きくて重負荷充放電時に容
量が小さくなるという問題があつた。However, the lithium secondary battery using the above-mentioned carbonaceous material as the negative electrode carrier has a problem that the polarization is large and the capacity becomes small at the time of heavy load charging / discharging.
【０００７】この発明は、上記従来の炭素質材料の問題
を解消し、負荷特性の良好なリチウム二次電池を提供す
ること、またこれを可能とする負極用カ―ボン電極を提
供することを目的としている。The present invention solves the above problems of conventional carbonaceous materials, provides a lithium secondary battery having good load characteristics, and provides a carbon electrode for a negative electrode that enables this. Has an aim.
【０００８】[0008]
【課題を解決するための手段】この発明者らは、上記目
的を達成するために鋭意検討した結果、従来の黒鉛類似
構造を有する炭素質などに特定の被覆層を設けて熱処理
して得られる炭素質材料を負極担持体として用いてみた
ところ、重負荷充放電時でも高容量のリチウム二次電池
が得られることを知り、この発明を完成するに至つた。Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, they are obtained by heat-treating a carbonaceous material having a conventional graphite-like structure with a specific coating layer. When a carbonaceous material was used as a negative electrode carrier, it was found that a high-capacity lithium secondary battery can be obtained even under heavy load charge / discharge, and the present invention was completed.
【０００９】すなわち、この発明の第１は、黒鉛類似構
造を有する炭素質または有機高分子物質の粒子状物にピ
ツチ被覆層を設けて熱処理ないし炭化処理してなる炭素
質材料の成形体からなることを特徴とするカ―ボン電極
に係るものであり、また、この発明の第２は、有機溶媒
にリチウム塩を溶解させた有機電解液を用いてなるリチ
ウム二次電池において、負極として上記のカ―ボン電極
を用いたことを特徴とするリチウム二次電池に係るもの
である。That is, the first aspect of the present invention comprises a molded body of a carbonaceous material obtained by providing a pitch coating layer on a particulate material of a carbonaceous or organic polymer substance having a graphite-like structure and subjecting it to heat treatment or carbonization treatment. The present invention relates to a carbon electrode, and a second aspect of the present invention is a lithium secondary battery using an organic electrolytic solution in which a lithium salt is dissolved in an organic solvent, wherein The present invention relates to a lithium secondary battery using a carbon electrode.
【００１０】[0010]
【発明の構成・作用】この発明における黒鉛類似構造を
有する炭素質としては、リチウムイオンをド―プ、脱ド
―プできるものであつて、ガラス状炭素類、有機高分子
化合物の焼成体、炭素繊維、活性炭などを用いることが
できる。また、有機高分子物質としては、フエノ―ル樹
脂、ポリアクリロニトリル樹脂、セルロ―ス樹脂、ポリ
アミド樹脂、ポリアミドイミド樹脂、ハロゲン化ビニル
樹脂などの常温で固形の樹脂を広く用いることができ
る。The carbonaceous material having a graphite-like structure according to the present invention is one that can be doped with lithium ions and dedoped, such as glassy carbons, a sintered body of an organic polymer compound, Carbon fiber, activated carbon or the like can be used. As the organic polymer substance, a wide range of solid resins at room temperature such as phenol resin, polyacrylonitrile resin, cellulose resin, polyamide resin, polyamideimide resin and vinyl halide resin can be widely used.
【００１１】このような炭素質または有機高分子物質か
らなる粒子状物は、平均粒子径が通常５〜１００μｍ程
度であるのがよい。この粒子状物の電気抵抗率は一般に
十分に小さくないため、これを負極担持体としたリチウ
ム二次電池は、重負荷充放電時での分極が大きくなつ
て、容量が低下する。The average particle size of the particulate matter composed of such a carbonaceous or organic polymer substance is usually about 5 to 100 μm. Since the electrical resistivity of the particulate matter is generally not sufficiently low, the lithium secondary battery using the particulate matter as a negative electrode carrier has a large polarization during heavy-load charging / discharging, resulting in a decrease in capacity.
【００１２】この発明では、上記問題の克服のため、上
記の粒子状物の表面にピツチ被覆層を設け、これを熱処
理ないし炭化処理して炭素質材料を構成させるようにし
たもので、この材料はそれ自体電気抵抗率（体積固有抵
抗）の低いものとなるため、これを負極担持体として用
いたリチウム二次電池は、重負荷充放電時での分極が小
さくなり、従来のような容量の低下が抑えられる。In the present invention, in order to overcome the above-mentioned problems, a pitch coating layer is provided on the surface of the above-mentioned particulate matter, which is heat-treated or carbonized to form a carbonaceous material. Has a low electric resistivity (volume specific resistance) by itself, so a lithium secondary battery using this as a negative electrode carrier has a small polarization during heavy-load charging / discharging, and has The decrease is suppressed.
【００１３】なお、従来構成の炭素質材料に対して導電
助材として金属粉などを混合し、これを電極材料として
用いてリチウム二次電池を作製すると、重負荷充放電時
での分極が小さくなつて、容量が増大してくるが、金属
粉などはリチウムのド―プ、脱ド―プ反応に関与しない
ため、上記この発明のものに比べると、体積あたりの容
量が小さく、十分な改善効果が得られない。When a lithium secondary battery is manufactured by mixing metal powder or the like as a conductive auxiliary material with a carbonaceous material having a conventional structure and using this as an electrode material, the polarization at the time of heavy load charging and discharging is small. The capacity increases, but since metal powder and the like do not participate in the lithium doping and de-doping reactions, the capacity per volume is smaller than that of the above-mentioned invention, which is a sufficient improvement. No effect.
【００１４】この発明において、ピツチ被覆層の形成
は、粒子状物に対し、有機物質の乾留で生成するタ―ル
を蒸留する際に得られる黒色の炭素質固形残留物、たと
えば、コ―ルタ―ルピツチ、木タ―ルピツチなどのピツ
チを塗布すればよく、その塗布量は、粒子状物に対し通
常５〜３０容量％程度とすればよい。In the present invention, the formation of the pitch coating layer is carried out by forming a black carbonaceous solid residue, for example, a coater, obtained when the tar produced by the dry distillation of the organic substance is distilled with respect to the particulate matter. Pitches such as lupitches and wood tarpitches may be applied, and the amount of application is usually about 5 to 30% by volume with respect to the particulate matter.
【００１５】この被覆層の形成後、通常８００〜２，５
００℃程度の温度で熱処理することにより、また粒子状
物が特に有機高分子物質からなるときはこれを上記同様
の温度で炭化処理することにより、目的とする炭素質材
料が得られる。After forming this coating layer, it is usually 800 to 2.5
The desired carbonaceous material can be obtained by heat treatment at a temperature of about 00 ° C., or when the particulate matter is made of an organic polymer material, it is carbonized at a temperature similar to the above.
【００１６】この発明のカ―ボン電極は、このようにし
て得た炭素質材料を用いて、常法により、所望形状の成
形体としたものである。一例として、上記の炭素質材料
粉末とそのバインダとなるポリテトラフルオロエチレン
粉末とを、水−アルコ―ル系混合溶媒に分散させたスラ
リ―を調製し、これをニツケル網などの金網上に塗布，
乾燥し、その後上記金網と一体に打ち抜き成形したうえ
で、所望厚さとなるまで加圧成形すればよい。The carbon electrode of the present invention is made into a molded product having a desired shape by a conventional method using the carbonaceous material thus obtained. As an example, a slurry is prepared by dispersing the above-mentioned carbonaceous material powder and polytetrafluoroethylene powder serving as a binder thereof in a water-alcohol mixed solvent, and applying the slurry onto a wire net such as a nickel net. ，
It may be dried, then punched and formed integrally with the wire net, and then pressure-formed to a desired thickness.
【００１７】図１は、上記のカ―ボン電極を負極とした
この発明のボタン型のリチウム二次電池の構造例を示し
たものである。図において、１はステンレス鋼からなる
皿型の負極缶、２はステンレス鋼からなる皿型の正極缶
であり、この両極缶１，２を向かい合わせ、両者の周縁
部を合成ゴムや合成樹脂などの弾性絶縁材料からなる環
状ガスケツト３を介在させて嵌合圧着することにより、
偏平な密閉容器を構成させている。FIG. 1 shows an example of the structure of the button type lithium secondary battery of the present invention in which the carbon electrode is used as a negative electrode. In the figure, 1 is a dish-shaped negative electrode can made of stainless steel, 2 is a dish-shaped positive electrode can made of stainless steel, and the bipolar cans 1 and 2 are opposed to each other, and the peripheral portions of both are made of synthetic rubber or synthetic resin. By fitting and crimping with the annular gasket 3 made of the elastic insulating material of
A flat closed container is constructed.
【００１８】この容器の内部には、負極缶１にステンレ
スネツトからなる集電体４を介して接合した前記特定の
成形体からなる負極５と、正極缶２にステンレスネツト
からなる集電体６を介して接合した正極７と、両極５，
７間に介在するセパレ―タ８および電解液吸収体９と
が、装てんされており、さらに有機溶媒にリチウム塩を
溶解させてなる有機電解液が注入されている。Inside the container, a negative electrode 5 made of the above-mentioned specific molded product joined to the negative electrode can 1 via a current collector 4 made of stainless steel, and a current collector 6 made of stainless steel in the positive electrode can 2. The positive electrode 7 joined via the
A separator 8 and an electrolyte solution absorber 9 which are interposed between 7 are loaded, and an organic electrolyte solution obtained by dissolving a lithium salt in an organic solvent is injected.
【００１９】上記の有機電解液において、有機溶媒とし
ては、エチレンカ―ボネ―ト、プロピレンカ―ボネ―
ト、１・２−ジメトキシエタン、γ−ブチロラクトン、
ジオキソランなどの極性溶媒が用いられる。また、リチ
ウム塩としては、ＬｉＣＦ3 ＳＯ3 、ＬｉＢＦ4 、Ｌｉ
ＣｌＯ4 、ＬｉＢφ4 （φはフエニル基）、ＬｉＰ
Ｆ6、ＬｉＡｓＦ6 などの各種塩が用いられる。In the above-mentioned organic electrolytic solution, as the organic solvent, ethylene carbonate, propylene carbonate
1, 1.2-dimethoxyethane, γ-butyrolactone,
A polar solvent such as dioxolane is used. Further, as the lithium salt, LiCF 3 SO 3 , LiBF 4 , Li
ClO 4 , LiBφ 4 (φ is a phenyl group), LiP
Various salts such as F 6 and LiAsF 6 are used.
【００２０】なお、この発明のカ―ボン電極からなる負
極は、図示したボタン型電池に限定されることなく、筒
型その他の種々の形態および構造のリチウム二次電池に
適用できることは言うまでもない。It is needless to say that the negative electrode comprising the carbon electrode of the present invention is not limited to the button type battery shown in the figure, but can be applied to lithium secondary batteries of various shapes and structures such as a tubular type.
【００２１】[0021]
【発明の効果】以上のように、この発明の前記特定の炭
素質材料の成形体からなるカ―ボン電極を、負極として
用いることにより、負荷特性の良好なリチウム二次電池
を得ることができる。As described above, by using the carbon electrode made of the molded body of the specific carbonaceous material of the present invention as the negative electrode, a lithium secondary battery having good load characteristics can be obtained. .
【００２２】[0022]
【実施例】つぎに、この発明の実施例を記載して、より
具体的に説明する。EXAMPLES Next, examples of the present invention will be described to explain more specifically.
【００２３】実施例１ 平均粒子径１０μｍの球状フエノ―ル樹脂に、コ―ルタ
―ルピツチを、上記樹脂に対し２０容量％の割合で塗布
したのち、１，０００℃で炭化処理して、炭素質材料を
得た。Example 1 A spherical phenol resin having an average particle diameter of 10 μm was coated with a coal pitch at a ratio of 20% by volume to the above resin, and then carbonized at 1,000 ° C. to obtain carbon. Obtained quality material.
【００２４】この炭素質材料３０ｇに、純水４．７ｇ、
ポリテトラフルオロエチレン粉末の６０重量％水分散液
１．５ｍｌ、イソプロピルアルコ―ル２．８ｍｌを加
え、３０分間撹拌して、スラリ―状とし、これを６０メ
ツシユのニツケル網の上に乾燥後の厚さが０．４mmとな
るように塗布し、２００℃で１時間乾燥した。これを直
径１０mm（面積０．７８５cm2 ）の大きさに打ち抜き、
１０トン／cm2 で加圧成形して、全体厚が０．３mmの成
形体からなるカ―ボン電極を作製した。To 30 g of this carbonaceous material, 4.7 g of pure water,
1.5 ml of a 60 wt% aqueous dispersion of polytetrafluoroethylene powder and 2.8 ml of isopropyl alcohol were added, and the mixture was stirred for 30 minutes to form a slurry, which was dried on a 60 mesh mesh net and dried. It was applied to a thickness of 0.4 mm and dried at 200 ° C. for 1 hour. Punch this into a size of 10 mm in diameter (area 0.785 cm 2 ),
It was pressure-molded at 10 ton / cm 2 to prepare a carbon electrode composed of a molded body having a total thickness of 0.3 mm.
【００２５】つぎに、上記のカ―ボン電極を負極とし、
正極としてＬｉＭｎＯ2 合剤からなる厚さ０．５mm、直
径１０mmの成形体を、セパレ―タとして微孔性ポリプロ
ピレンフイルムを、電解液吸収体としてポリプロピレン
不織布を、有機電解液としてエチレンカ―ボネ―トと１
・２−ジメトキシエタンとの容量比１：１の混合溶媒に
ＬｉＣＦ3 ＳＯ3 を０．６モル／ｌ溶解させてなる溶液
を、環状ガスケツトとしてポリプロピレン製のものを、
それぞれ使用して、図１に示す構造のボタン型のリチウ
ム二次電池を作製した。Next, using the carbon electrode as the negative electrode,
A molded body made of LiMnO 2 mixture having a thickness of 0.5 mm and a diameter of 10 mm is used as a positive electrode, a microporous polypropylene film is used as a separator, a polypropylene nonwoven fabric is used as an electrolytic solution absorber, and an ethylene carbonate is used as an organic electrolytic solution. And 1
A solution of LiCF 3 SO 3 dissolved in a mixed solvent of 2-dimethoxyethane in a volume ratio of 1: 1 in an amount of 0.6 mol / l, and a cyclic gasket made of polypropylene,
Using each of them, a button type lithium secondary battery having a structure shown in FIG. 1 was produced.
【００２６】実施例２ 平均粒子径１０μｍの球状フエノ―ル樹脂に、コ―ルタ
―ルピツチを、上記樹脂に対し１０容量％の割合で塗布
したのち、１，０００℃で炭化処理して、炭素質材料を
得た。この炭素質材料を用いた以外は、実施例１と同様
にしてカ―ボン電極を作製し、またこの電極を負極とし
て実施例１と同様にして、図１に示す構造のボタン型の
リチウム二次電池を作製した。Example 2 A spherical phenol resin having an average particle diameter of 10 μm was coated with a coal pitch at a ratio of 10% by volume to the above resin, and then carbonized at 1,000 ° C. to obtain carbon. Obtained quality material. A carbon electrode was prepared in the same manner as in Example 1 except that this carbonaceous material was used, and this electrode was used as a negative electrode in the same manner as in Example 1 to prepare a button-type lithium battery having the structure shown in FIG. A secondary battery was produced.
【００２７】実施例３ 平均粒子径１０μｍの球状フエノ―ル樹脂に、コ―ルタ
―ルピツチを、上記樹脂に対し５容量％の割合で塗布し
たのち、１，０００℃で炭化処理して、炭素質材料を得
た。この炭素質材料を用いた以外は、実施例１と同様に
してカ―ボン電極を作製し、またこの電極を負極として
実施例１と同様にして、図１に示す構造のボタン型のリ
チウム二次電池を作製した。Example 3 A spherical phenol resin having an average particle diameter of 10 μm was coated with a coater pitch at a ratio of 5% by volume to the above resin, and then carbonized at 1,000 ° C. to obtain carbon. Obtained quality material. A carbon electrode was prepared in the same manner as in Example 1 except that this carbonaceous material was used, and this electrode was used as a negative electrode in the same manner as in Example 1 to prepare a button-type lithium battery having the structure shown in FIG. A secondary battery was produced.
【００２８】比較例１ 平均粒子径１０μｍの球状フエノ―ル樹脂を１，０００
℃で炭化処理して、炭素質材料とし、この材料を用いて
実施例１と同様にしてカ―ボン電極を作製し、またこの
電極を負極として実施例１と同様にして、図１に示す構
造のボタン型のリチウム二次電池を作製した。Comparative Example 1 1,000 parts of spherical phenol resin having an average particle diameter of 10 μm was used.
The carbonaceous material was carbonized at ℃ to prepare a carbon electrode using this material in the same manner as in Example 1, and this electrode was used as a negative electrode in the same manner as in Example 1 and shown in FIG. A button type lithium secondary battery having a structure was produced.
【００２９】実施例４ 平均粒子径１０μｍのポリアクリロニトリル系（以下、
ＰＡＮ系という）炭素繊維（１，０００℃炭化品）に、
コ―ルタ―ルピツチを、上記炭素繊維に対し２０容量％
の割合で塗布したのち、１，０００℃で炭化処理して、
炭素質材料を得た。この炭素質材料を用いた以外は、実
施例１と同様にしてカ―ボン電極を作製し、またこの電
極を負極として実施例１と同様にして、図１に示す構造
のボタン型のリチウム二次電池を作製した。Example 4 A polyacrylonitrile-based material having an average particle diameter of 10 μm (hereinafter, referred to as
PAN-based) carbon fiber (carbonized products at 1,000 ° C)
20% by volume of the coal pitch with respect to the carbon fiber
, Then carbonize at 1,000 ° C,
A carbonaceous material was obtained. A carbon electrode was prepared in the same manner as in Example 1 except that this carbonaceous material was used, and this electrode was used as a negative electrode in the same manner as in Example 1 to prepare a button-type lithium battery having the structure shown in FIG. A secondary battery was produced.
【００３０】実施例５ 平均粒子径１０μｍのＰＡＮ系炭素繊維（１，０００℃
炭化品）に、コ―ルタ―ルピツチを、上記炭素繊維に対
し１０容量％の割合で塗布したのち、１，０００℃で炭
化処理して、炭素質材料を得た。この炭素質材料を用い
た以外は、実施例１と同様にしてカ―ボン電極を作製
し、またこの電極を負極として実施例１と同様にして、
図１に示す構造のボタン型のリチウム二次電池を作製し
た。Example 5 PAN-based carbon fiber having an average particle size of 10 μm (1,000 ° C.)
A carbonaceous material) was coated with a coral pitch at a ratio of 10% by volume with respect to the carbon fiber, and then carbonized at 1,000 ° C. to obtain a carbonaceous material. A carbon electrode was produced in the same manner as in Example 1 except that this carbonaceous material was used, and this electrode was used as a negative electrode in the same manner as in Example 1,
A button type lithium secondary battery having the structure shown in FIG. 1 was produced.
【００３１】比較例２ 平均粒子径１０μｍのＰＡＮ系炭素繊維（１，０００℃
炭化品）をさらに１，０００℃で炭化処理して、炭素質
材料とし、この材料を用いて実施例１と同様にしてカ―
ボン電極を作製し、またこの電極を負極として実施例１
と同様にして、図１に示す構造のボタン型のリチウム二
次電池を作製した。Comparative Example 2 PAN-based carbon fiber having an average particle diameter of 10 μm (1,000 ° C.)
(Carbonized product) is further carbonized at 1,000 ° C. to obtain a carbonaceous material, and this material is used in the same manner as in Example 1
A Bon electrode was prepared, and this electrode was used as a negative electrode in Example 1.
A button type lithium secondary battery having the structure shown in FIG. 1 was produced in the same manner as in.
【００３２】以上の実施例１〜５および比較例１，２の
各カ―ボン電極について、その電気抵抗率ρ∞を調べ
た。また、実施例１〜５および比較例１，２の各リチウ
ム二次電池について、０．５ｍＡ／cm2 および２ｍＡ／
cm2 の定電流で充放電したときの放電容量を測定した。
これらの結果を、後記の表１に示す。なお、上記の電気
抵抗率ρ∞は、下記の方法で測定した。The electrical resistivity ρ∞ of each carbon electrode of Examples 1 to 5 and Comparative Examples 1 and 2 was examined. For each of the lithium secondary batteries of Examples 1 to 5 and Comparative Examples 1 and 2, 0.5 mA / cm 2 and 2 mA / cm 2
The discharge capacity was measured when the battery was charged and discharged at a constant current of cm 2 .
The results are shown in Table 1 below. The above electrical resistivity ρ∞ was measured by the following method.
【００３３】＜カ―ボン電極の電気抵抗率ρ∞の測定＞
測定試料を１５０℃で３時間真空乾燥したのち、赤松式
粉末炭材電気抵抗測定器を用いて、つぎの式（１），
（２）に示すように、圧縮圧力Ｐに対する比抵抗ρを測
定し、１／√Ｐ対ρのプロツトから、Ｐを無限大に外挿
して、電気抵抗率ρ∞を求めた。<Measurement of electric resistivity ρ∞ of carbon electrode>
After vacuum drying the measurement sample at 150 ° C. for 3 hours, the following formula (1),
As shown in (2), the resistivity ρ with respect to the compression pressure P was measured, and P was infinitely extrapolated from the plot of 1 / √P vs. ρ to obtain the electrical resistivity ρ∞.
【００３４】 σd ＝２√Ｐ／（√πＨ×σv ） … （１） σd ＝ｒc ´／ｒ×σv … （２） （Ｐ→∞のとき、σd ＝σv ） σd ：見掛けの導電率（Ｓcm-1） σv ：粒子の実体の導電率（Ｓcm-1） Ｐ ：圧縮圧力（Kg／cm2 ） Ｈ ：粒子の実体の硬度 ｒc ´：接触面の有効半径＝ｒc ＋Δｒc （cm） Δｒc ：接触部への水分の吸着による接触円半径ｒc の
増加分（cm）Σ d = 2√P / (√πH × σ v ) (1) σ d = r c ′ / r × σ v (2) (when P → ∞, σ d = σ v ) σ d: apparent conductivity (Scm -1) σ v: conductivity of the substance of the particle (Scm -1) P: compression pressure (Kg / cm 2) H: hardness r c entity of the particles': contact surface effective Radius = r c + Δr c (cm) Δr c : Increase in contact circle radius r c due to adsorption of water on the contact area (cm)
【００３５】[0035]
【表１】 [Table 1]
【００３６】上記の試験結果からも明らかなように、こ
の発明の実施例１〜３および実施例４，５の各リチウム
二次電池は、それぞれ、対応する従来の比較例１および
比較例２のリチウム二次電池に比べ、負荷特性にすぐれ
ていることがわかる。As is clear from the above test results, the lithium secondary batteries of Examples 1 to 3 and Examples 4 and 5 of the present invention are the same as those of the corresponding conventional Comparative Example 1 and Comparative Example 2, respectively. It can be seen that the load characteristics are superior to those of the lithium secondary battery.
【図１】本発明のリチウム二次電池の一例を示す断面図
である。FIG. 1 is a cross-sectional view showing an example of a lithium secondary battery of the present invention.
１：負極缶 ２：正極缶 ５：負極 ７：正極 ８：セパレ―タ ９：電解液吸収体 1: Negative electrode can 2: Positive electrode can 5: Negative electrode 7: Positive electrode 8: Separator 9: Electrolyte absorber
Claims (2)
高分子物質の粒子状物にピツチ被覆層を設けて熱処理な
いし炭化処理してなる炭素質材料の成形体からなること
を特徴とするカ―ボン電極。1. A car made of a carbonaceous material formed by heat-treating or carbonizing a particulate coating of carbonaceous or organic polymer having a graphite-like structure with a pitch coating layer. Bon electrode.
電解液を用いてなるリチウム二次電池において、負極と
して請求項１に記載のカ―ボン電極を用いたことを特徴
とするリチウム二次電池。2. A lithium secondary battery using an organic electrolytic solution in which a lithium salt is dissolved in an organic solvent, wherein the carbon electrode according to claim 1 is used as a negative electrode. battery.
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|---|---|---|---|
| JP18455692A JP3310695B2 (en) | 1992-06-17 | 1992-06-17 | Carbon electrode and lithium secondary battery using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18455692A JP3310695B2 (en) | 1992-06-17 | 1992-06-17 | Carbon electrode and lithium secondary battery using the same |
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| Publication Number | Publication Date |
|---|---|
| JPH065288A true JPH065288A (en) | 1994-01-14 |
| JP3310695B2 JP3310695B2 (en) | 2002-08-05 |
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ID=16155278
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996004688A1 (en) * | 1994-08-04 | 1996-02-15 | Mitsubishi Chemical Corp. | Electrode material for nonaqueous solvent secondary cell and method of manufacturing the same |
| WO1999001904A1 (en) * | 1997-07-04 | 1999-01-14 | Hitachi Powdered Metals Co., Ltd. | Graphite powder for negative electrode of lithium ion secondary cell and method of production thereof |
| JP2001176516A (en) * | 1999-12-15 | 2001-06-29 | Sumitomo Chem Co Ltd | Positive electrode mix paste for lithium secondary battery and lithium secondary battery |
| JP2003109594A (en) * | 2001-10-01 | 2003-04-11 | Showa Denko Kk | Electrode material, manufacturing method of the same, electrode for battery using the same, and battery using the electrode |
-
1992
- 1992-06-17 JP JP18455692A patent/JP3310695B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996004688A1 (en) * | 1994-08-04 | 1996-02-15 | Mitsubishi Chemical Corp. | Electrode material for nonaqueous solvent secondary cell and method of manufacturing the same |
| KR100392899B1 (en) * | 1994-08-04 | 2003-11-28 | 미쓰비시 가가꾸 가부시키가이샤 | Non-aqueous solvent secondary battery electrode material and manufacturing method thereof |
| WO1999001904A1 (en) * | 1997-07-04 | 1999-01-14 | Hitachi Powdered Metals Co., Ltd. | Graphite powder for negative electrode of lithium ion secondary cell and method of production thereof |
| US6759169B1 (en) | 1997-07-04 | 2004-07-06 | Hitachi Powdered Metals Co., Ltd. | Graphite powder for negative electrode of lithium ion secondary cell and method of production thereof |
| JP2001176516A (en) * | 1999-12-15 | 2001-06-29 | Sumitomo Chem Co Ltd | Positive electrode mix paste for lithium secondary battery and lithium secondary battery |
| JP4649692B2 (en) * | 1999-12-15 | 2011-03-16 | 住友化学株式会社 | Positive electrode mixture paste for lithium secondary battery and lithium secondary battery |
| JP2003109594A (en) * | 2001-10-01 | 2003-04-11 | Showa Denko Kk | Electrode material, manufacturing method of the same, electrode for battery using the same, and battery using the electrode |
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| Publication number | Publication date |
|---|---|
| JP3310695B2 (en) | 2002-08-05 |
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