JPH05234593A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH05234593A JPH05234593A JP4041956A JP4195692A JPH05234593A JP H05234593 A JPH05234593 A JP H05234593A JP 4041956 A JP4041956 A JP 4041956A JP 4195692 A JP4195692 A JP 4195692A JP H05234593 A JPH05234593 A JP H05234593A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- battery
- carbonaceous material
- secondary battery
- volume expansion
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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】本発明は、非水電解液二次電池に
関し、特にコイン型の非水電解液二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a coin type non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術】電解液に非水電解液を使用した、いわゆ
る非水電解液電池は自己放電の少ない保存性に優れた電
池として知られている。そして、このような非水電解液
電池は、たとえば正極缶、正極ペレット、セパレータ、
負極ペレット、負極集電体、負極缶が積層されたコイン
型形状とされて、５〜１０年という長期間使用が要求さ
れる電子腕時計や種々のメモリーバックアップ用電源と
して広く利用されるようになっている。2. Description of the Related Art A so-called non-aqueous electrolyte battery in which a non-aqueous electrolyte is used as an electrolyte is known as a battery having less self-discharge and excellent storage stability. Then, such a non-aqueous electrolyte battery, for example, a positive electrode can, a positive electrode pellet, a separator,
It has a coin-shaped shape in which negative electrode pellets, negative electrode current collectors, and negative electrode cans are laminated, and is widely used as an electronic wristwatch and various memory backup power sources that require long-term use for 5 to 10 years. ing.
【０００３】ところで、これら従来使用されている非水
電解液電池は、通常一次電池仕様であるが、長期間経済
的に使用できるように、再充電可能な二次電池仕様化へ
の要望が多く、このため各方面で非水電解液二次電池の
研究，開発が進められている。By the way, these conventionally used non-aqueous electrolyte batteries usually have primary battery specifications, but there are many demands for rechargeable secondary battery specifications so that they can be economically used for a long period of time. Therefore, research and development of non-aqueous electrolyte secondary batteries are being promoted in various fields.
【０００４】たとえば非水電解液二次電池としては、負
極にリチウムを用いたリチウム二次電池が挙げられる。
しかしながら、このリチウム二次電池は、充放電サイク
ル繰り返しに伴い、リチウムがデンドライト状に結晶成
長し、セパレータの孔、繊維の空隙を通過して正極に到
達し内部短絡を起こしたり、リチウムが不活性化し、粉
末状に析出する等の欠点があり、このことが実用化への
障害になっている。As a non-aqueous electrolyte secondary battery, for example, there is a lithium secondary battery using lithium as a negative electrode.
However, in this lithium secondary battery, with repeated charge and discharge cycles, lithium grows in a dendrite-like crystal form, passes through the holes in the separator and the voids in the fiber, reaches the positive electrode, and causes an internal short circuit, or the lithium is inactive. However, there are drawbacks such as formation of powder and precipitation in powder form, which is an obstacle to practical use.
【０００５】そこで、さらに、負極材料にリチウムやリ
チウムイオンをドープ、脱ドープできるコークス類、グ
ラファイト類や有機高分子焼成体等のような炭素材料を
使用するコイン型非水電解液二次電池が提案されてい
る。この負極材料に炭素質材料を使用する非水電解液二
次電池は、充放電サイクル繰り返しによるリチウムのデ
ンドライト状結晶化もなく、電池電圧が高く、高エネル
ギー密度が得られることから大きな期待がよせられてい
る。Therefore, a coin type non-aqueous electrolyte secondary battery using a carbon material such as coke, graphite or a sintered body of an organic polymer, which can be doped or dedoped with lithium or lithium ions as a negative electrode material, is further provided. Proposed. The non-aqueous electrolyte secondary battery that uses a carbonaceous material as the negative electrode material has high expectations because it has a high battery voltage and high energy density without dendrite crystallization of lithium due to repeated charge and discharge cycles. Has been.
【０００６】ここで、上記非水電解液二次電池に使用さ
れる炭素質材料としては、例えば特開昭６２−１２２０
６６号公報、あるいは特開昭６２−９０８６３号公報等
に開示されるように、通常は（００２）面の面間隔が
３．４０〜３．６０Å、真密度が１．７０〜２．２０ｇ
／ｃｍ3 程度のものが用いられている。Here, examples of the carbonaceous material used in the above non-aqueous electrolyte secondary battery include, for example, JP-A-62-1220.
No. 66 or JP-A-62-90863, the (002) plane spacing is usually 3.40 to 3.60Å and the true density is 1.70 to 2.20 g.
/ Cm 3 is used.
【０００７】しかしながら、上記炭素質材料は、リチウ
ムのドープ可能量が不十分で、電池のエネルギー密度を
決定する大きな要因である炭素の単位重量当たりの容量
（ｍＡｈ／ｇ）が理論値の半分程度に過ぎないことが解
ってきた。（理論的には、炭素原子６個に対してリチウ
ム原子１個の割合でドープされる。）However, the carbonaceous material is insufficient in the amount of lithium that can be doped, and the capacity per unit weight of carbon (mAh / g), which is a major factor in determining the energy density of the battery, is about half of the theoretical value. It turned out that it was nothing more than. (Theoretically, one carbon atom is doped to six carbon atoms.)
【０００８】そこで、リチウムドープ可能量が大きい炭
素質材料として、（００２）面の面間隔が３．７０Å以
上、真密度１．７ｇ／ｃｍ3 未満であり、且つ空気気流
中に於ける示差熱分析で７００℃以上に発熱ピークを有
しない炭素質材料の使用が検討されている。この炭素質
材料を使用すれば、サイクル寿命に優れるだけでなく放
電容量も大きな非水電解液二次電池が得られることが解
っている。（特開昭６３−２１７９５号公報）Therefore, as a carbonaceous material having a large amount of lithium that can be doped, the (002) plane has an interplanar spacing of 3.70 Å or more, a true density of less than 1.7 g / cm 3 , and a differential heat in an air stream. The use of carbonaceous materials, which have no exothermic peak above 700 ° C. in analysis, is being considered. It has been found that the use of this carbonaceous material makes it possible to obtain a non-aqueous electrolyte secondary battery which has not only excellent cycle life but also large discharge capacity. (Japanese Patent Laid-Open No. 63-21795)
【０００９】[0009]
【発明が解決しようとする課題】ところが、コイン型あ
るいはボタン型の非水電解液二次電池においては、負極
と負極集電体の接触は炭素質材料のリチウムドープによ
る体積膨張によって電池缶内に内圧が生じて確実とされ
るが、上記炭素質材料はリチウムドープ可能量が大きい
反面、リチウムドープによる体積膨張が殆どない。した
がって、上記炭素質材料を使用した場合には、接触不良
となり、電池性能に不具合が生じるといった不都合が生
じる。However, in a coin-type or button-type non-aqueous electrolyte secondary battery, the contact between the negative electrode and the negative electrode current collector is caused in the battery can by volume expansion due to lithium doping of the carbonaceous material. Although the internal pressure is surely generated, the carbonaceous material has a large amount of lithium that can be doped, but has little volume expansion due to lithium doping. Therefore, when the above-mentioned carbonaceous material is used, a contact failure occurs, which causes a problem in battery performance.
【００１０】そこで、本発明はこのような従来の実情に
鑑みて提案されたものであり、サイクル寿命が長く、大
放電容量であるとともに接触不良が生じない非水電解液
二次電池を提供することを目的とする。Therefore, the present invention has been proposed in view of such conventional circumstances, and provides a non-aqueous electrolyte secondary battery having a long cycle life, a large discharge capacity, and no contact failure. The purpose is to
【００１１】[0011]
【課題を解決するための手段】上述の目的を達成するた
めに、本発明の非水電解液二次電池は、（００２）面の
面間隔が３．７０Å以上、真密度が１．７０ｇ／ｃｍ3
未満であり、且つ空気気流中に於ける示差熱分析で７０
０℃以上に発熱ピークを有しない炭素質材料に他の炭素
質材料を混合してなる負極材料と結着剤よりなる負極ペ
レットと、正極材料と結着剤よりなる正極ペレットを有
してなる非水電解液二次電池において、上記負極ペレッ
トが、上記負極材料の単位重量当たりの容量で３８０ｍ
Ａｈ／ｇ充電したときに５〜６０％の体積膨張を生じる
ことを特徴とするものである。In order to achieve the above object, the non-aqueous electrolyte secondary battery of the present invention has a (002) plane spacing of 3.70Å or more and a true density of 1.70 g / cm 3
And less than 70 by differential thermal analysis in air flow
A negative electrode pellet made of a negative electrode material obtained by mixing a carbonaceous material having no exothermic peak above 0 ° C. with another carbonaceous material and a binder, and a positive electrode pellet made of a positive electrode material and a binder. In the non-aqueous electrolyte secondary battery, the negative electrode pellet has a capacity per unit weight of the negative electrode material of 380 m.
It is characterized by causing a volume expansion of 5 to 60% when charged with Ah / g.
【００１２】本発明においては、長サイクル寿命，大放
電容量を得るとともに負極ペレットをリチウムドープに
よって体積増大するものとなし、これにより接触不良を
防止するために、負極ペレットに含有する負極材料とし
て（００２）面の面間隔が３．７０Å以上、真密度が
１．７０ｇ／ｃｍ3 未満であり、且つ空気気流中に於け
る示差熱分析で７００℃以上に発熱ピークを有しない炭
素質材料に、リチウムのドープにより体積膨張を生じる
他の炭素質材料を添加してなるものを使用する。In the present invention, it is assumed that the long-term cycle life and large discharge capacity are obtained and the volume of the negative electrode pellet is increased by doping with lithium. As a result, in order to prevent contact failure, the negative electrode material contained in the negative electrode pellet is ( A carbonaceous material having a 002) plane spacing of 3.70 Å or more and a true density of less than 1.70 g / cm 3 and having no exothermic peak at 700 ° C. or more in a differential thermal analysis in an air stream, A material obtained by adding another carbonaceous material that causes volume expansion by doping with lithium is used.
【００１３】すなわち、上記形態的パラメータを有する
炭素質材料は、リチウムドープ可能量が大きいため、長
サイクル寿命，大放電容量を得る上では適しているが、
リチウムがドープされたときの体積膨張率が小さい。し
たがって、このような炭素質材料を含有する負極ペレッ
トはリチウムドープによる体積増大がほとんどない。一
方、上記形態的パラメータを有する炭素質材料にリチウ
ムドープによる体積膨張率が大きい炭素質材料を添加し
てなる負極材料を使用すると、体積膨張効果が補足さ
れ、リチウムドープ能力をほとんど損なうことなく電池
内圧上昇の点でも十分な負極ペレットが得られる。That is, the carbonaceous material having the above-mentioned morphological parameters is suitable for obtaining a long cycle life and a large discharge capacity, because the amount of lithium that can be doped is large.
The volume expansion coefficient when doped with lithium is small. Therefore, the negative electrode pellet containing such a carbonaceous material hardly increases in volume due to lithium doping. On the other hand, when a negative electrode material obtained by adding a carbonaceous material having a large volume expansion coefficient due to lithium doping to the carbonaceous material having the above-mentioned morphological parameters is used, the volume expansion effect is complemented, and the lithium doping ability is hardly impaired in the battery. Sufficient negative electrode pellets can be obtained in terms of increasing the internal pressure.
【００１４】リチウムのドープによって体積膨張を生じ
る炭素質材料としては、コークス類（石油コークス、石
炭コークス等）、カーボンブラック（アセチレンブラッ
ク等）、黒鉛類、有機高分子焼成体（有機高分子材料を
５００℃以上の適当な温度で不活性ガス気流中、あるい
は真空中で焼成したもの）、炭素繊維等が挙げられる
が、これら炭素質材料のうちでも、リチウムのドープ、
脱ドープできる量が大きく、サイクル毎に不活性化する
リチウム量が少ない炭素質材料を選択して使用すること
が望ましい。Examples of carbonaceous materials that cause volume expansion by doping with lithium include cokes (petroleum coke, coal coke, etc.), carbon black (acetylene black, etc.), graphites, organic polymer fired bodies (organic polymer materials Examples of such carbonaceous materials include those fired in an inert gas stream or in a vacuum at an appropriate temperature of 500 ° C. or higher), and among these carbonaceous materials, lithium doping,
It is desirable to select and use a carbonaceous material having a large amount that can be dedoped and a small amount of lithium that is inactivated in each cycle.
【００１５】なお、上記負極ペレットの体積膨張量は、
接触をより確実なものとするためには、ある程度の大き
さが必要であるが、あまり大きくなると電解液の収容ス
ペースが小さくなり、内部抵抗の増大、放電容量の低下
を招くこととなる。したがって、体積膨張剤として添加
する炭素質材料の種類，添加量等は、リチウムを負極材
料の単位重量当たり３８０ｍＡｈ／ｇで充電したときの
負極ペレットの体積膨張率が、５〜６０％、より好まし
くは、６〜５０％、さらに好ましくは１０〜３５％とな
るように調整する必要がある。また、体積膨張剤として
添加する炭素質材料の添加量があまり多くなると上記形
態的パラメータを有する炭素質材料の量が少なくなり、
リチウムドープ能力が十分に発揮されない虞れがあるこ
とから、炭素質材料の添加量は、負極材料に対して５０
重量％以下に抑えることが好ましい。The volume expansion of the negative electrode pellet is
In order to make the contact more reliable, a certain size is required, but if it is too large, the storage space for the electrolytic solution becomes small, which causes an increase in internal resistance and a decrease in discharge capacity. Therefore, the type and amount of the carbonaceous material added as the volume expanding agent is preferably such that the volume expansion coefficient of the negative electrode pellet when lithium is charged at 380 mAh / g per unit weight of the negative electrode material is 5 to 60%, more preferably. Needs to be adjusted to 6 to 50%, more preferably 10 to 35%. Further, when the amount of the carbonaceous material added as the volume expanding agent is too large, the amount of the carbonaceous material having the above-mentioned morphological parameters becomes small,
Since the lithium doping ability may not be fully exhibited, the addition amount of the carbonaceous material is 50% with respect to the negative electrode material.
It is preferable to control the content to be not more than weight%.
【００１６】一方、本発明の非水電解液二次電池におい
て、正極ペレットに含有する正極活物質としては、Ｌｉ
ＣｏＯ2 とグラファイトパウダーおよびＰＴＦＥパウダ
ーの混合物を圧縮成型して正極ペレットとして用いた
が、他に二酸化マンガン、五酸化バナジウム、硫化鉄の
ごとき遷移金属の酸化物、カルコゲン化合物、さらには
これら酸化物、カルコゲン化合物とリチウムとの複合化
合物を用いることが可能である。On the other hand, in the non-aqueous electrolyte secondary battery of the present invention, the positive electrode active material contained in the positive electrode pellets is Li.
A mixture of CoO 2 and graphite powder and PTFE powder was compression molded and used as a positive electrode pellet. Besides, manganese dioxide, vanadium pentoxide, oxides of transition metals such as iron sulfide, chalcogen compounds, and these oxides, It is possible to use a complex compound of a chalcogen compound and lithium.
【００１７】また、電解液に使用する有機溶媒として
は、特に限定されるものではないが、例えばプロピレン
カーボネート、エチレンカーボネート、ジエチルカーボ
ネート、１，２−ジメトキシエタン、１，２−ジエトキ
シエタン、γ−ブチロラクトン、テトラヒドロフラン、
１，３−ジオキソラン、４−メチル−１，３−ジオキソ
ラン、ジエジルエーテル、スルホラン、メチルスルホラ
ン、アセトニトリル、プロピオニトリル等の単独もしく
は二種類以上の混合溶媒が使用できる。The organic solvent used in the electrolytic solution is not particularly limited, but for example, propylene carbonate, ethylene carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ. -Butyrolactone, tetrahydrofuran,
A single solvent or a mixed solvent of two or more kinds of 1,3-dioxolane, 4-methyl-1,3-dioxolane, diezyl ether, sulfolane, methylsulfolane, acetonitrile, propionitrile and the like can be used.
【００１８】電解質も従来より公知のものがいずれも使
用でき、ＬｉＣｌＯ4 、ＬｉＡｓＦ6 、ＬｉＰＦ6 、Ｌ
ｉＢＦ4 、ＬｉＢ（Ｃ6 Ｈ5 ）4 、ＬｉＣｌ、ＬｉＢ
ｒ、ＣＨ3 ＳＯ3 Ｌｉ、ＣＦ3 ＳＯ3 Ｌｉ等がある。Any known electrolyte can be used as the electrolyte, and LiClO 4 , LiAsF 6 , LiPF 6 , L
iBF 4 , LiB (C 6 H 5 ) 4 , LiCl, LiB
r, CH 3 SO 3 Li, CF 3 SO 3 Li and the like.
【００１９】[0019]
【作用】コイン型非水電解液二次電池において、負極ペ
レットに含有する負極材料として（００２）面の面間隔
が３．７０Å以上、真密度が１．７０ｇ／ｃｍ3 未満で
あり、且つ空気気流中に於ける示差熱分析で７００℃以
上に発熱ピークを有しない炭素質材料にリチウムのドー
プによって体積膨張が生じる他の炭素質材料を添加して
なるものを使用すると、負極ペレットは、上記形態的パ
ラメータを有する炭素質材料によって優れたリチウムド
ープ能力が付加されるとともに、充電によって十分体積
増大するものとなる。ここで、負極ペレットの体積増大
率が、５〜６０％となるように体積膨張剤となる炭素質
材料の種類，添加量を調整すると、電池内圧が適正なも
のとなり、負極と負極集電体の接触が十分確実になり、
電解液の収容スペースも確保され、良好な電池特性が得
られるようになる。In the coin-type non-aqueous electrolyte secondary battery, the negative electrode material contained in the negative electrode pellets has a (002) plane spacing of 3.70 Å or more, a true density of less than 1.70 g / cm 3 , and air. When a carbonaceous material having no exothermic peak at 700 ° C. or higher in an air stream added with another carbonaceous material that causes volume expansion due to lithium doping is used, the negative electrode pellet is The carbonaceous material having a morphological parameter adds an excellent lithium doping ability, and also has a sufficient volume increase by charging. Here, if the kind and addition amount of the carbonaceous material serving as the volume expanding agent are adjusted so that the volume increase rate of the negative electrode pellets is 5 to 60%, the battery internal pressure becomes appropriate, and the negative electrode and the negative electrode current collector. Contact is sufficiently secure,
A space for accommodating the electrolytic solution is secured, and good battery characteristics can be obtained.
【００２０】[0020]
【実施例】本発明の好適な実施例について図面を参照し
ながら説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will be described with reference to the drawings.
【００２１】実験例１ 図１に本実施例で作成するコイン型非水電解液二次電池
を示す。 Experimental Example 1 FIG. 1 shows a coin type non-aqueous electrolyte secondary battery prepared in this example.
【００２２】まず、正極ペレット３を以下のようにして
作製した。まず、炭酸リチウム０．５モルと炭酸コバル
ト１モルを混合し、９００℃の空気中で５時間焼成して
正極活物質となるＬｉＣｏＯ2 を得た。そして、このＬ
ｉＣｏＯ2 ８５重量部に導電剤としてグラファイト１２
重量部、結合剤としてポリテトラフルオロエチレンパウ
ダー３重量部とを均質に混合して予備成型した後、この
予備成型された正極ペレット上にアルミニウム粉末（平
均粒径４５μｍ）を重量０．０３ｇ充填して圧縮成型す
ることにより外径１５．３ｍｍ、高さ１．１９ｍｍ、重
量０．７５５ｇ正極ペレット３を作製した。First, the positive electrode pellet 3 was manufactured as follows. First, 0.5 mol of lithium carbonate and 1 mol of cobalt carbonate were mixed and fired in air at 900 ° C. for 5 hours to obtain LiCoO 2 as a positive electrode active material. And this L
Graphite 12 as a conductive agent in 85 parts by weight of iCoO 2
1 part by weight and 3 parts by weight of polytetrafluoroethylene powder as a binder are mixed homogeneously and preformed, and then 0.03 g of aluminum powder (average particle diameter 45 μm) is filled on the preformed positive electrode pellets. By compression molding, the positive electrode pellet 3 having an outer diameter of 15.3 mm, a height of 1.19 mm and a weight of 0.755 g was produced.
【００２３】一方、負極ペレット２は以下のようにして
作製した。出発原料として石油ピッチを用い、これに酸
素を含む官能基を１０〜２０重量％導入（いわゆる酸素
架橋）した後、不活性ガス雰囲気中１０００℃で焼成し
てガラス状炭素に近い性質を持った難黒鉛化性炭素質材
料を得た。この材料についてＸ線回折測定を行った結果
（００２）面の面間隔が３．７６Åであった。またピク
ノメータ方に準じて真密度を測定したところ１．６２ｇ
／ｃｍ3 であった。更に、空気気流中において示差熱分
析を行ったところ、最高温度６５０℃付近に存在し、７
００℃以上には発熱ピークは見られなかった。On the other hand, the negative electrode pellet 2 was produced as follows. Petroleum pitch was used as a starting material, and 10 to 20% by weight of a functional group containing oxygen was introduced into this (so-called oxygen cross-linking), followed by firing at 1000 ° C. in an inert gas atmosphere to have properties similar to glassy carbon. A non-graphitizable carbonaceous material was obtained. As a result of X-ray diffraction measurement of this material, the spacing between (002) planes was 3.76Å. The true density measured according to the Pycnometer method is 1.62g.
/ Cm 3 . Further, when a differential thermal analysis was performed in an air stream, it was found that the maximum temperature was around 650 ° C, and
No exothermic peak was observed above 00 ° C.
【００２４】この軟黒鉛化炭素質材料８７重量部に、添
加剤として炭素繊維（昭和電工社製，商品名 気相法炭
素繊維ＶＧＣＦ）を３重量部加えて負極材料とし、この
負極材料に結合剤としてポリフッ化ビニリデン１０重量
部を加え均質に混合し、これに分散剤であるＮ−メチル
−２−ピロリドンを加え乾燥したものを圧縮成型するこ
とで、外径１５．６ｍｍ、高さ０．７４ｍｍ、重量０．
１５６ｇの負極ペレット２を作製した。To 87 parts by weight of the soft graphitized carbonaceous material, 3 parts by weight of carbon fiber (trade name: vapor grown carbon fiber VGCF manufactured by Showa Denko KK) was added as an additive to prepare a negative electrode material, which was bonded to the negative electrode material. As an agent, 10 parts by weight of polyvinylidene fluoride was added and mixed homogeneously, N-methyl-2-pyrrolidone as a dispersant was added thereto, and the dried product was compression-molded to give an outer diameter of 15.6 mm and a height of 0. 74 mm, weight 0.
156 g of the negative electrode pellet 2 was produced.
【００２５】次にこの負極ペレット２を予め負極缶１に
スポット溶接された外径１５．８ｍｍ、内径１５．６ｍ
ｍ、高さ０．７３のステンレス製円筒状集電体リング４
に入れ、その上にマイクロポーラスフィルムセパレータ
７を重ね、さらにプラスチック製の封口ガスケット５を
セパレータ７を介してその上部に置き、この上から電解
液を滴下した。そして、この上に前述の正極ペレット３
をアルミニウム層をセパレータと対向しないかたちで載
置させ、その上にアルミニウム−ステンレス−ニッケル
の３層からなる正極外装缶６をかぶせ、その端をカシメ
てシールし外径２０ｍｍ、高さ２．８ｍｍのコイン型非
水電解液二次電池（電池１）を作製した。Next, this negative electrode pellet 2 was spot-welded to the negative electrode can 1 in advance, the outer diameter being 15.8 mm and the inner diameter being 15.6 m.
m, height 0.73 stainless steel cylindrical current collector ring 4
Then, the microporous film separator 7 was placed thereon, and the sealing gasket 5 made of plastic was placed on the upper part thereof via the separator 7, and the electrolytic solution was dripped from above. Then, on the positive electrode pellet 3
Is placed in such a manner that the aluminum layer does not face the separator, a positive electrode outer can 6 made of three layers of aluminum-stainless-nickel is placed on the separator, and the end is caulked and sealed to have an outer diameter of 20 mm and a height of 2.8 mm. A coin type non-aqueous electrolyte secondary battery (Battery 1) was manufactured.
【００２６】なお、電解液としてはプロピレンカーボネ
ートとジエチルカーボネートを体積比で１：１の割合で
混合した溶媒にＬｉＰＦ6 を１モル／１の割合で溶解さ
せた有機電解液を用いた。As the electrolytic solution, an organic electrolytic solution prepared by dissolving LiPF 6 at a ratio of 1 mol / 1 in a solvent in which propylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 by volume was used.
【００２７】実験例２ 上記軟黒鉛化炭素質材料８５重量部に炭素繊維５重量部
を添加してなるものを負極材料として使用する以外は実
施例１と同様にしてコイン型非水電解液二次電池（電池
２）を作製した。 Experimental Example 2 A coin type non-aqueous electrolyte solution 2 was prepared in the same manner as in Example 1 except that 85 parts by weight of the above-mentioned soft graphitized carbonaceous material and 5 parts by weight of carbon fiber were used as the negative electrode material. A secondary battery (battery 2) was produced.
【００２８】実験例３ 上記軟黒鉛化炭素質材料８０重量部に炭素繊維１０重量
部を添加してなるものを負極材料として使用する以外は
実施例１と同様にしてコイン型非水電解液二次電池（電
池３）を作製した。 Experimental Example 3 A coin type non-aqueous electrolyte solution 2 was prepared in the same manner as in Example 1 except that 80 parts by weight of the soft graphitized carbonaceous material and 10 parts by weight of carbon fiber were used as the negative electrode material. A secondary battery (Battery 3) was produced.
【００２９】実験例４ 炭素繊維を添加していない軟黒鉛化炭素質材料を負極材
料として使用する以外は実施例１と同様にしてコイン型
非水電解液二次電池（電池４）を作製した。 Experimental Example 4 A coin type non-aqueous electrolyte secondary battery (battery 4) was prepared in the same manner as in Example 1 except that a soft graphitized carbonaceous material containing no carbon fiber was used as the negative electrode material. ..
【００３０】負極材料の体積膨張率の検討 このようにして作製された電池１〜電池４について、
０．９４ｍＡの電流で上限電圧４．０Ｖとして充電した
時の負極ペレット体積変化を調査した。負極材料１ｇ当
たりの充電電気量と負極ペレット体積膨張率の関係を図
２に示す。なお、体積膨張率は負極集電体の厚さと直径
の変化量より求めたものである。 Examination of Volume Expansion Coefficient of Negative Electrode Material Regarding the batteries 1 to 4 thus prepared,
The change in the negative electrode pellet volume when charged at a current of 0.94 mA with an upper limit voltage of 4.0 V was investigated. FIG. 2 shows the relationship between the amount of charged electricity per 1 g of the negative electrode material and the negative electrode pellet volume expansion coefficient. The volume expansion coefficient is obtained from the amount of change in the thickness and diameter of the negative electrode current collector.
【００３１】図２において充電電気量３８０ｍＡｈ／ｇ
の場合で見ると、軟黒鉛炭素質材料のみよりなる負極材
料を使用する電池４では、負極ペレットの体積膨張率は
約４％であり、非常に少ないことがわかる。これに対し
て、炭素質材料に添加剤として炭素繊維を添加してなる
負極材料を使用する場合においては、負極ペレットの体
積膨張率は、炭素繊維３％添加の電池１で約１６％、炭
素繊維５％添加の電池２で約４９％、炭素繊維１０％添
加の電池３で約１００％と炭素繊維の添加量の増大に伴
って大きくなる。In FIG. 2, the amount of electricity charged is 380 mAh / g.
In the case of No. 4, in the battery 4 using the negative electrode material composed only of the soft graphite carbonaceous material, the volume expansion coefficient of the negative electrode pellet is about 4%, which is very small. On the other hand, when a negative electrode material obtained by adding carbon fiber to the carbonaceous material as an additive is used, the volume expansion coefficient of the negative electrode pellet is about 16% in the battery 1 containing 3% carbon fiber, The battery 2 containing 5% of fiber has about 49%, and the battery 3 containing 10% of carbon fiber has about 100%, which increases as the amount of carbon fiber added increases.
【００３２】したがって、これらの結果から、（００
２）面の面間隔が３．７０Å以上、真密度が１．７０ｇ
／ｃｍ3 未満であり、且つ空気気流中に於ける示差熱分
析で７００℃以上に発熱ピークを有しない炭素質材料に
リチウムドープによる体積膨張率が大きい炭素質材料を
添加してなる負極材料を使用することは、体積増大の大
きい負極ペレットを得る上で有効であることがわかっ
た。Therefore, from these results, (00
2) Face spacing is 3.70Å or more, and true density is 1.70g.
/ Cm 3 and a negative electrode material obtained by adding a carbonaceous material having a large volume expansion coefficient due to lithium doping to a carbonaceous material having no exothermic peak at 700 ° C. or more in a differential thermal analysis in an air stream. It was found that the use thereof is effective in obtaining a negative electrode pellet with a large volume increase.
【００３３】電池特性の検討 次に、負極材料に体積膨張剤として炭素質材料を添加す
ることによる電池特性への効果について検討した。ま
ず、電池１〜電池４について、充電電圧４．０Ｖ、温度
６０℃にて１２日間連続して電圧を印加する耐電圧性試
験をおこなった。そして、試験前と試験後の電池内部抵
抗値、１．９ｍＡで２．５Ｖの終止電圧まで放電させた
時の放電容量をそれぞれ測定した。その結果を表１に示
す。 Examination of Battery Characteristics Next, the effect on the battery characteristics by adding a carbonaceous material as a volume expanding agent to the negative electrode material was examined. First, the batteries 1 to 4 were subjected to a withstand voltage test in which a voltage was continuously applied for 12 days at a charging voltage of 4.0 V and a temperature of 60 ° C. Then, before and after the test, the internal resistance value of the battery was measured, and the discharge capacity at the time of discharging to the final voltage of 2.5 V at 1.9 mA was measured. The results are shown in Table 1.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表１からわかるように、比較例電池１（体
積膨張率４％）では、試験前の内部抵抗値が８．１Ω、
容量が３１ｍＡｈであるが、試験後の電池内部抵抗値は
１８．８Ωと２倍以上に上昇しており、容量は９ｍＡｈ
と大きく低下している。これは負極ペレットの体積膨張
率が低い為に負極集電体リングとの電気的接触が不十分
であることが原因であると考えられる。As can be seen from Table 1, in Comparative Example Battery 1 (volume expansion coefficient 4%), the internal resistance value before the test was 8.1Ω,
Although the capacity is 31 mAh, the internal resistance value of the battery after the test is 18.8Ω, which is more than doubled, and the capacity is 9 mAh.
And is greatly reduced. It is considered that this is because the negative electrode pellets have a low volume expansion coefficient and thus insufficient electrical contact with the negative electrode current collector ring.
【００３６】電池１（体積膨張率１６％）では、試験前
の内部抵抗値が５．６Ω、容量が２９ｍＡｈであるのに
対し、試験後の電池内部抵抗値は８．３Ωと上昇が少な
く、容量も２２ｍＡｈと試験前の７５％以上を維持して
いる。これは負極ペレットの体積膨張率が高い為に負極
集電体リングとの電気的接触が十分に得られている為で
ある。In Battery 1 (volume expansion coefficient 16%), the internal resistance value before the test was 5.6Ω and the capacity was 29 mAh, whereas the internal resistance value after the test was 8.3Ω, which was a small increase. The capacity is 22 mAh, which is more than 75% before the test. This is because the negative electrode pellet has a high volume expansion coefficient, and therefore, sufficient electrical contact with the negative electrode current collector ring is obtained.
【００３７】一方、電池２（体積膨張率４９％）では試
験前の内部抵抗値が１２．５Ω、容量が１８ｍＡｈであ
ったが、試験後においては、電池内部抵抗値が２１．１
Ωと内部抵抗値の上昇が大きく、容量も１０ｍＡｈと容
量保持率が低くなっている。ここで、電池２は、電池１
に比べ負極ペレットの体積膨張率が大きいにもかかわら
ず初期電池内部抵抗値が高く容量が小さい、又試験後で
の電池内部抵抗上昇も大きく、容量保持率も低くなって
いる。これは、負極ペレットの体積膨張率が大きすぎる
ために、電解液量の収容スペースが小さくなり、電解液
量が不足したためである。On the other hand, in Battery 2 (volume expansion coefficient 49%), the internal resistance value before the test was 12.5Ω and the capacity was 18 mAh, but after the test, the internal resistance value was 21.1.
The increase of Ω and the internal resistance value is large, and the capacity is 10 mAh and the capacity retention rate is low. Here, the battery 2 is the battery 1
Although the negative electrode pellet has a large volume expansion coefficient, the initial battery internal resistance value is high and the capacity is small, the battery internal resistance increase after the test is large, and the capacity retention ratio is low. This is because the volume expansion coefficient of the negative electrode pellet was too large, so that the space for accommodating the amount of the electrolytic solution became small and the amount of the electrolytic solution was insufficient.
【００３８】電池３（体積膨張率１０３％）において、
初期内部抵抗値が６９．３Ωと非常に高く、容量も２ｍ
Ａｈと殆ど放電できない状態であるのも、電池２と同じ
く電解液量の不足によるためである。In Battery 3 (volume expansion coefficient 103%),
Very high initial internal resistance of 69.3Ω and capacity of 2m
The reason why the battery is in a state in which almost no discharge is possible with Ah is due to the shortage of the amount of electrolyte as in the battery 2.
【００３９】したがって、コイン型非水電解液二次電池
においては、負極ペレットの体積膨張が小さすぎると負
極集電体との電気的接触が不十分となり、反対に体積膨
張率が高すぎても電解液量の不足が発生してしまうこと
から最適な負極ペレットの体積膨張条件が要求されるこ
とがわかる。Therefore, in the coin type non-aqueous electrolyte secondary battery, if the volume expansion of the negative electrode pellet is too small, electrical contact with the negative electrode current collector becomes insufficient, and conversely if the volume expansion coefficient is too high. It can be seen that the optimum volume expansion condition of the negative electrode pellet is required because the amount of the electrolyte solution becomes insufficient.
【００４０】そこで、図３に負極ペレットの体積膨張率
と容量保持率の関係を示すが、このように、容量保持率
は、負極ペレットの体積膨張が全くない場合には３０％
程度と低く、体積膨張率の増大に伴って大きくなるが、
体積膨張率があまり大きくなると逆に低下しており、負
極ペレットの体積膨張率が電池特性に大きく影響する。
すなわち、放電容量を十分に維持するためには、負極ペ
レットの体積膨張率は５〜６０％、好ましくは６〜５０
％、更に好ましくは１０〜３５％が望ましいことがわか
る。FIG. 3 shows the relationship between the volume expansion rate of the negative electrode pellets and the capacity retention rate. Thus, the capacity retention rate is 30% when the negative electrode pellets have no volume expansion.
Although it is low, it increases as the volume expansion rate increases,
On the contrary, when the volume expansion coefficient becomes too large, the volume expansion coefficient decreases, and the volume expansion coefficient of the negative electrode pellet greatly affects the battery characteristics.
That is, in order to maintain a sufficient discharge capacity, the negative electrode pellet has a volume expansion coefficient of 5 to 60%, preferably 6 to 50.
%, More preferably 10 to 35% is desirable.
【００４１】[0041]
【発明の効果】以上の説明から明らかなように、本発明
の非水電解液二次電池においては、負極ペレットに含有
する負極材料として、（００２）面の面間隔が３．７０
Å以上、真密度が１．７０ｇ／ｃｍ3 未満であり、且つ
空気気流中に於ける示差熱分析で７００℃以上に発熱ピ
ークを有しない炭素質材料にリチウムのドープによって
体積膨張が生じる炭素質材料を添加してなるものを使用
するとともに、上記負極ペレットの充電による体積膨張
率を適正なものとしている。したがって、電池内部での
加圧が充分に保たれ、電気的接触が良好になり、好容量
で重負荷特性に優れ、且つ高温特性にも優れた極めて信
頼性ある非水電解液二次電池を得ることが可能であり、
工業的価値は大である。As is clear from the above description, in the non-aqueous electrolyte secondary battery of the present invention, the negative electrode material contained in the negative electrode pellets has a (002) plane spacing of 3.70.
Carbonaceous material having volumetric expansion of Å or more, true density of less than 1.70 g / cm 3 and having no exothermic peak at 700 ° C or more in differential thermal analysis in an air stream due to lithium doping A material obtained by adding a material is used, and the volume expansion coefficient of the negative electrode pellet due to charging is made proper. Therefore, an extremely reliable non-aqueous electrolyte secondary battery with sufficient pressure inside the battery, good electrical contact, good capacity, excellent heavy load characteristics, and excellent high temperature characteristics can be obtained. Is possible to obtain,
The industrial value is great.
【図１】本発明に非水電解液二次電池の一構成例を示す
断面図である。FIG. 1 is a cross-sectional view showing a configuration example of a non-aqueous electrolyte secondary battery according to the present invention.
【図２】負極材料単位重量当たりの充電電気量と負極ペ
レットの体積膨張率を示す特性図である。FIG. 2 is a characteristic diagram showing the amount of charge electricity per unit weight of the negative electrode material and the volume expansion coefficient of the negative electrode pellet.
【図３】負極ペレットの体積膨張率と容量保持率の関係
を示す特性図である。FIG. 3 is a characteristic diagram showing the relationship between the volume expansion rate and the capacity retention rate of negative electrode pellets.
１・・・負極缶 ２・・・負極ペレット ３・・・正極ペレット ４・・・負極集電体 ６・・・正極缶 1 ... Negative electrode can 2 ... Negative electrode pellet 3 ... Positive electrode pellet 4 ... Negative electrode current collector 6 ... Positive electrode can
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年４月２８日[Submission date] April 28, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２１[Correction target item name] 0021
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２１】実験例１ 図１に本実施例で作製するコイン型非水電解液二次電池
を示す。 Experimental Example 1 FIG. 1 shows a coin type non-aqueous electrolyte secondary battery produced in this example.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２３[Name of item to be corrected] 0023
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２３】一方、負極ペレット２は以下のようにして
作製した。出発原料として石油ピッチを用い、これに酸
素を含む官能基を１０〜２０重量％導入（いわゆる酸素
架橋）した後、不活性ガス雰囲気中１０００℃で焼成し
て ガラス状炭素に近い性質を持った難黒鉛化性炭素質
材料を得た。この材料につい てＸ線回折測定を行った
結果（００２）面の面間隔が３．７６Åであった。また
ピクノメータ法に準じて真密度を測定したところ１．
６２ｇ／ｃｍ３であった。更に、空気気流中において示
差熱分析を行ったところ、最高温度６５０℃付近に存在
し、７００℃以上には発熱ピークは見られなかった。On the other hand, the negative electrode pellet 2 was produced as follows. Petroleum pitch was used as a starting material, and 10 to 20% by weight of a functional group containing oxygen was introduced (so-called oxygen cross-linking) into the pitch, followed by firing at 1000 ° C. in an inert gas atmosphere to have properties similar to glassy carbon. A non-graphitizable carbonaceous material was obtained. As a result of X-ray diffraction measurement of this material, the spacing between (002) planes was 3.76Å. The true density was measured according to the pycnometer method.
It was 62 g / cm 3 . Further, when a differential thermal analysis was carried out in an air stream, it was present at a maximum temperature of around 650 ° C, and no exothermic peak was observed above 700 ° C.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Correction target item name] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２４】この難黒鉛化炭素質材料８７重量部に、添
加剤として炭素繊維（昭和電工社製，商品名 気相法炭
素繊維ＶＧＣＦ）を３重量部加えて負極材料とし、この
負極 材料に結合剤としてポリフッ化ビニリデン１０重
量部を加え均質に混合し、これ に分散剤であるＮ−メ
チル−２−ピロリドンを加え乾燥したものを圧縮成型す
る ことで、外径１５．６ｍｍ、高さ０．７４ｍｍ、重
量０．１５６ｇの負極ペレッ ト２を作製した。To 87 parts by weight of this non-graphitizable carbonaceous material, 3 parts by weight of carbon fiber (trade name: vapor phase carbon fiber VGCF manufactured by Showa Denko KK) was added as an additive to prepare a negative electrode material, which was bonded to the negative electrode material. As an agent, 10 parts by weight of polyvinylidene fluoride was added and mixed homogeneously, and N-methyl-2-pyrrolidone, which is a dispersant, was added thereto and dried, and the resulting mixture was compression-molded to give an outer diameter of 15.6 mm and a height of 0. A negative electrode pellet 2 having a diameter of 74 mm and a weight of 0.156 g was prepared.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２７[Name of item to be corrected] 0027
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２７】実験例２ 上記難黒鉛化炭素質材料８５重量部に炭素繊維５重量部
を添加してなるものを負極材料として使用する以外は実
施例１と同様にしてコイン型非水電解液二次電池（電池
２）を作製した。 Experimental Example 2 A coin type non-aqueous electrolyte solution 2 was prepared in the same manner as in Example 1 except that 85 parts by weight of the non-graphitizable carbonaceous material and 5 parts by weight of carbon fiber were used as the negative electrode material. A secondary battery (battery 2) was produced.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２８[Correction target item name] 0028
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２８】実験例３ 上記難黒鉛化炭素質材料８０重量部に炭素繊維１０重量
部を添加してなるものを負極材料として使用する以外は
実施例１と同様にしてコイン型非水電解液二次電池（電
池３）を作製した。 Experimental Example 3 A coin type non-aqueous electrolyte solution 2 was prepared in the same manner as in Example 1 except that 80 parts by weight of the non-graphitizable carbonaceous material and 10 parts by weight of carbon fiber were used as the negative electrode material. A secondary battery (Battery 3) was produced.
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２９[Name of item to be corrected] 0029
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２９】実験例４ 炭素繊維を添加していない難黒鉛化炭素質材料を負極材
料として使用する以外は実施例１と同様にしてコイン型
非水電解液二次電池（電池４）を作製した。 Experimental Example 4 A coin type non-aqueous electrolyte secondary battery (battery 4) was produced in the same manner as in Example 1 except that a non-graphitizable carbonaceous material containing no carbon fiber was used as the negative electrode material. ..
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３１[Correction target item name] 0031
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３１】図２において充電電気量３８０ｍＡｈ／ｇ
の場合で見ると、難黒鉛炭素質材料のみよりなる負極材
料を使用する電池４では、負極ペレットの体積膨張率は
約４％であり、非常に少ないことがわかる。これに対し
て、炭素質材料に添加剤として炭素繊維を添加してなる
負極材料を使用する場合においては、負極ペレットの体
積膨張率は、炭素繊維３％添加の電池１で約１６％、炭
素繊維５％添加の電池２で約４９％、炭素繊維１０％添
加の電池３で約１００％と炭素繊維の添加量の増大に伴
って大きくなる。In FIG. 2, the amount of electricity charged is 380 mAh / g.
In the case of No. 4, in the battery 4 using the negative electrode material composed only of the non-graphite carbonaceous material, the volume expansion coefficient of the negative electrode pellet is about 4%, which is very small. On the other hand, when a negative electrode material obtained by adding carbon fiber to the carbonaceous material as an additive is used, the volume expansion coefficient of the negative electrode pellet is about 16% in the battery 1 containing 3% carbon fiber, The battery 2 containing 5% of fiber has about 49%, and the battery 3 containing 10% of carbon fiber has about 100%, which increases as the amount of carbon fiber added increases.
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４１[Correction target item name] 0041
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４１】[0041]
【発明の効果】以上の説明から明らかなように、本発明
の非水電解液二次電池においては、負極ペレットに含有
する負極材料として、（００２）面の面間隔が３．７０
Å以上、真密度が１．７０ｇ／ｃｍ３未満であり、且つ
空気気流中に於ける示差熱分析で７００℃以上に発熱ピ
ークを有しない炭素質材料にリチウムのドープによって
体積膨張が生じる炭素質材料を添加してなるものを使用
するとともに、上記負極ペレットの充電による体積膨張
率を適正なものとしている。したがって、電池内部での
加圧が充分に保たれ、電気的接触が良好になり、高容量
で重負荷特性に優れ、且つ高温特性にも優れた極めて信
頼性ある非水電解液二次電池を得ることが可能であり、
工業的価値は大である。As is clear from the above description, in the non-aqueous electrolyte secondary battery of the present invention, the negative electrode material contained in the negative electrode pellets has a (002) plane spacing of 3.70.
Carbonaceous material whose volume density is Å or more and whose true density is less than 1.70 g / cm 3 and which has no exothermic peak at 700 ° C or more in differential thermal analysis in an air stream due to lithium doping. A material obtained by adding a material is used, and the volume expansion coefficient of the negative electrode pellet due to charging is made proper. Therefore, an extremely reliable non-aqueous electrolyte secondary battery, in which sufficient pressure is maintained inside the battery, good electrical contact is achieved, high capacity, excellent heavy load characteristics, and excellent high temperature characteristics, is provided. Is possible to obtain,
The industrial value is great.
Claims (1)
上、真密度が１．７０ｇ／ｃｍ3 未満であり、且つ空気
気流中に於ける示差熱分析で７００℃以上に発熱ピーク
を有しない炭素質材料に他の炭素質材料を混合してなる
負極材料と結着剤よりなる負極ペレットと、正極材料と
結着剤よりなる正極ペレットを有してなる非水電解液二
次電池において、 上記負極ペレットが、上記負極材料の単位重量当たりの
容量で３８０ｍＡｈ／ｇ充電したときに５〜６０％の体
積膨張を生じることを特徴とする非水電解液二次電池。1. The (002) plane has an interplanar spacing of 3.70 Å or more, a true density of less than 1.70 g / cm 3 , and has an exothermic peak at 700 ° C. or more in differential thermal analysis in an air stream. In a non-aqueous electrolyte secondary battery comprising a negative electrode pellet made of a binder and a negative electrode material formed by mixing another carbonaceous material with a carbonaceous material, and a positive electrode pellet made of a positive electrode material and a binder. The non-aqueous electrolyte secondary battery, wherein the negative electrode pellet causes a volume expansion of 5 to 60% when charged at 380 mAh / g with a capacity per unit weight of the negative electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04195692A JP3458389B2 (en) | 1992-01-31 | 1992-01-31 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04195692A JP3458389B2 (en) | 1992-01-31 | 1992-01-31 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05234593A true JPH05234593A (en) | 1993-09-10 |
| JP3458389B2 JP3458389B2 (en) | 2003-10-20 |
Family
ID=12622647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04195692A Expired - Fee Related JP3458389B2 (en) | 1992-01-31 | 1992-01-31 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3458389B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000033402A1 (en) * | 1998-12-02 | 2000-06-08 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell and its charging method |
| US6605386B1 (en) | 1998-12-02 | 2003-08-12 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| US6653019B1 (en) | 1998-06-03 | 2003-11-25 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| US6821675B1 (en) | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
| US6824920B1 (en) | 1997-06-03 | 2004-11-30 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| JP2005056827A (en) * | 2003-07-23 | 2005-03-03 | Matsushita Electric Ind Co Ltd | Coin-shaped all solid battery |
-
1992
- 1992-01-31 JP JP04195692A patent/JP3458389B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6824920B1 (en) | 1997-06-03 | 2004-11-30 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| US6653019B1 (en) | 1998-06-03 | 2003-11-25 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| US6821675B1 (en) | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
| WO2000033402A1 (en) * | 1998-12-02 | 2000-06-08 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell and its charging method |
| US6605386B1 (en) | 1998-12-02 | 2003-08-12 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| JP2005056827A (en) * | 2003-07-23 | 2005-03-03 | Matsushita Electric Ind Co Ltd | Coin-shaped all solid battery |
| JP4617105B2 (en) * | 2003-07-23 | 2011-01-19 | パナソニック株式会社 | Coin-type all-solid-state battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3458389B2 (en) | 2003-10-20 |
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