JP2516741B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP2516741B2 JP2516741B2 JP61007754A JP775486A JP2516741B2 JP 2516741 B2 JP2516741 B2 JP 2516741B2 JP 61007754 A JP61007754 A JP 61007754A JP 775486 A JP775486 A JP 775486A JP 2516741 B2 JP2516741 B2 JP 2516741B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- secondary battery
- layer surface
- carbon fiber
- aqueous electrolyte
- 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.)
- Expired - Fee Related
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
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
【発明の詳細な説明】 本発明は、特殊な炭素層面の配向構造をもつ微細な炭
素繊維を正極活物質として用いることにより、充放電電
気量の向上を可能にした二次電池に関するものである。Description: TECHNICAL FIELD The present invention relates to a secondary battery capable of improving the amount of charge and discharge electricity by using a fine carbon fiber having a special carbon layer surface orientation structure as a positive electrode active material. .
従来、塊状、板状あるいは繊維状の黒鉛質炭素材料が
非水電解質二次電池の正極活物質として働くことはよく
知られている。しかしながら、それら活物質の単位重量
当りの電気的エネルギー量（充放電電気量）は必ずしも
高くなく、これは実用化の最大の障害となっている。例
えば、3000℃で熱処理した熱分解黒鉛を正極物質、リチ
ウムを負極物質、プロピレンカーボネート中に溶解させ
た過塩素酸リチウムを電解液とした二次電池の充放電電
気量は、炭素1g当り85±５クーロン程度（約100Wh/kg炭
素）が限界とされている（T.Ohzuku,Z.Takehara,S.Yosh
izawa,Denki Kaguku,Vol.46,No.8,pp.438-441（197
8））。また、黒鉛繊維の織布を電極とした同様の二次
電池では、放電電気量は炭素1g当り24クーロン以下にす
ぎない（例えば、Y.Matsuda,M.Morita,H.Katsuma,J.Ele
ctrochem.Soc.,Vol.131,No.1,pp.104-106（1984））。Conventionally, it is well known that a block-shaped, plate-shaped, or fibrous graphitic carbon material acts as a positive electrode active material of a non-aqueous electrolyte secondary battery. However, the amount of electric energy (charge and discharge electricity amount) per unit weight of these active materials is not necessarily high, which is the biggest obstacle to practical use. For example, the amount of charge and discharge of a secondary battery using a pyrolytic graphite heat-treated at 3000 ° C. as a positive electrode material, lithium as a negative electrode material, and lithium perchlorate dissolved in propylene carbonate as an electrolyte solution is 85 ± 1 g of carbon. The limit is about 5 coulombs (about 100Wh / kg carbon) (T.Ohzuku, Z.Takehara, S.Yosh
izawa, Denki Kaguku, Vol.46, No.8, pp.438-441 (197
8)). Moreover, in a similar secondary battery using a woven cloth of graphite fiber as an electrode, the discharge electricity amount is 24 coulombs or less per 1 g of carbon (for example, Y. Matsuda, M. Morita, H. Katsuma, J. Ele.
ctrochem.Soc., Vol.131, No.1, pp.104-106 (1984)).
本発明者らは、この低いエネルギー密度は黒鉛質炭素
の構造に原因があると考えて検討した結果、本電池の発
明に至ったものである。The inventors of the present invention considered that this low energy density was caused by the structure of the graphitic carbon, and as a result, studied, the invention of the present battery was achieved.
すなわち、例えば前述の過塩素酸リチウムを電解質と
する場合の電池反応は、 nC＋LiClO4→Cn・ClO4＋Li+＋e- と表わされる。この場合の充放電電気量は正極での層間
化合物Cn・ClO4の組成ｎに依存するが、これまでｎ＝96
の値が定説となっており、これから計算すれば、充放電
電気量は炭素1g当り84クーロンとなる。つまり、炭素原
子96個に対して過塩素酸イオン１個しか放電しない。こ
の原因は、従来の電極材料は比較的大きな黒鉛成型体あ
るいは繊維径５〜20μｍの比較的大きな繊維状黒鉛繊維
を用いたものであるので、これらの黒鉛質炭素電極の内
部まで十分に層間化合物が生成しないためであると考え
られる。それゆえ、より容易に層間化合物を作り得る構
造の炭素材料として、炭素層面が繊維軸に対してある角
度をもって円錐状または角錐状に配向し、かつ繊維径が
0.1〜３μｍの微細な黒鉛質炭素繊維を選び、これを正
極活物質とすれば、繊維全体が層間化合物を作るように
なって、充放電電気量の大きな二次電池が開発できるも
のと期待される。本発明はこのような考察にもとづいて
検討されたものである。That is, for example, the battery reaction when using the above-mentioned lithium perchlorate as an electrolyte is expressed as nC + LiClO 4 → Cn · ClO 4 + Li + + e − . The amount of charge and discharge in this case depends on the composition n of the intercalation compound Cn · ClO 4 at the positive electrode.
The value of is the established theory, and if calculated from this, the amount of charge and discharge electricity will be 84 coulombs per 1 g of carbon. That is, for 96 carbon atoms, only one perchlorate ion is discharged. The reason for this is that the conventional electrode material uses a relatively large graphite molded body or a relatively large fibrous graphite fiber having a fiber diameter of 5 to 20 μm. Is not generated. Therefore, as a carbon material having a structure that can more easily form an intercalation compound, the carbon layer surface is oriented in a conical or pyramidal shape at an angle to the fiber axis, and the fiber diameter is
It is expected that if a fine graphite carbon fiber of 0.1 to 3 μm is selected and this is used as the positive electrode active material, the entire fiber will form an intercalation compound, and a secondary battery with a large amount of charge and discharge electricity can be developed. It The present invention has been studied based on such considerations.
すなわち、本発明は、電解質を溶解した有機溶媒に電
極が接触して設けられている非水電解質二次電池におい
て、炭素繊維軸に対してその炭素層面が２ないし45度の
傾斜角度で配向して、中空構造に形成され、かつ0.1な
いし３μｍの繊維径を有する炭素繊維が正極活物質とし
て使用されていることを特徴とする非水電解質二次電池
にあり、また、本発明は、電解質を溶解した有機溶媒に
電極が接触して設けられている非水電解質二次電池にお
いて、炭素繊維軸に対してその炭素層面が２ないし45度
の傾斜角度で配向して、中空構造に形成され、かつ0.1
ないし３μｍの繊維径を有する炭素繊維が正極活物質と
して使用されている二次電池において、炭素繊維軸に対
する炭素層面が、円錐状又は角錐状に形成されているこ
とを特徴とする非水電解質二次電池にある。That is, the present invention relates to a non-aqueous electrolyte secondary battery in which an electrode is provided in contact with an organic solvent in which an electrolyte is dissolved, and the carbon layer surface is oriented at an inclination angle of 2 to 45 degrees with respect to the carbon fiber axis. And a carbon fiber having a hollow structure and having a fiber diameter of 0.1 to 3 μm is used as a positive electrode active material, which is a non-aqueous electrolyte secondary battery. In a non-aqueous electrolyte secondary battery in which an electrode is provided in contact with a dissolved organic solvent, the carbon layer surface is oriented at an inclination angle of 2 to 45 degrees with respect to the carbon fiber axis to form a hollow structure, And 0.1
In a secondary battery in which carbon fibers having a fiber diameter of 3 to 3 μm are used as a positive electrode active material, the carbon layer surface with respect to the carbon fiber axis is formed in a conical shape or a pyramidal shape. It is in the next battery.
本発明に用いられる炭素繊維、例えば、黒鉛質炭素繊
維の一例についての長さ方向断面構造の概略が、第１図
に示されている。この炭素繊維１は、中空構造を有する
ものであり、図には、炭素層面２と共に中空部３が示さ
れている。An outline of the longitudinal cross-sectional structure of an example of carbon fiber used in the present invention, for example, graphite carbon fiber, is shown in FIG. The carbon fiber 1 has a hollow structure, and the carbon layer surface 2 and the hollow portion 3 are shown in the drawing.
このような特殊な炭素層面２の配向構造をもつ炭素繊
維１は、炭化水素を硫化水素及び水素と共に1000℃以上
の温度で熱分解することにより得られ、繊維軸４に対し
て炭素層面２が10〜45°の角度で円錐状に配向した構造
をもつ黒鉛質炭素繊維１であり、この炭素繊維の多く
は、中空状に形成され、繊維径ｄは0.1〜３μｍであ
る。さらにこれを不活性ガス流通下2000〜3000℃で黒鉛
化処理すると、黒鉛化性はさらによくなり、炭素層面２
が繊維軸４に対し２〜20°の角度で円錐状または角錐状
に配向した構造となる。したがって配向角度αつまり炭
素繊維軸４に対する炭素層面２の傾斜角度は２〜45°の
角度となる。The carbon fiber 1 having such a special orientation structure of the carbon layer surface 2 is obtained by thermally decomposing hydrocarbons with hydrogen sulfide and hydrogen at a temperature of 1000 ° C. or higher, and the carbon layer surface 2 is attached to the fiber axis 4. This is a graphitic carbon fiber 1 having a structure oriented conically at an angle of 10 to 45 °, and most of this carbon fiber is formed in a hollow shape, and the fiber diameter d is 0.1 to 3 μm. Furthermore, when this is graphitized at 2000 to 3000 ° C. under an inert gas flow, the graphitization is further improved, and the carbon layer surface 2
Has a conical or pyramidal orientation at an angle of 2 to 20 ° with respect to the fiber axis 4. Therefore, the orientation angle α, that is, the inclination angle of the carbon layer surface 2 with respect to the carbon fiber axis 4 is an angle of 2 to 45 °.
このような特殊な配向構造をもつ黒鉛質炭素繊維はそ
のまま適当な金属の網で包んで、二次電池の正極として
用いることができる。また、このような特殊な配向構造
をもつ黒鉛質炭素繊維を適当なバインダーを用いて棒
状、シート状、フェルト状、紙状等に成形して、二次電
池の正極として用いてもよく、とくにその形状には限定
されない。The graphitic carbon fiber having such a special orientation structure can be used as it is as a positive electrode of a secondary battery by wrapping it in a net of a suitable metal. Further, the graphite carbon fiber having such a special orientation structure may be molded into a rod shape, a sheet shape, a felt shape, a paper shape or the like using an appropriate binder, and may be used as a positive electrode of a secondary battery. The shape is not limited.
本発明において、もう一方の電極すなわち負極の活物
質としては、アルカリ金属、アルカリ土類金属及び周期
律表第３族の金属、あるいはこれらを含む合金等が好ま
しく、例えばリチウム、ナトリウム、カリウム、マグネ
シウム、カルシウム、アルミニウム等とそれらの合金を
挙げることができ、なかでも高い起電力が得られかつ電
池の軽量化という点からリチウムとその合金が好ましい
が、本発明は上述のような特殊な構造の炭素繊維を用い
ることにあるので、とくに負極活物質の種類に限定され
るものではない。In the present invention, the other electrode, that is, the active material of the negative electrode is preferably an alkali metal, an alkaline earth metal, a metal of Group 3 of the periodic table, or an alloy containing these, such as lithium, sodium, potassium and magnesium. , Calcium, aluminum, and alloys thereof can be mentioned. Among them, lithium and its alloys are preferable from the viewpoints of obtaining a high electromotive force and reducing the weight of a battery, but the present invention has a special structure as described above. Since carbon fibers are used, the type of negative electrode active material is not particularly limited.
また、本発明において用いられる電解質としては、過
塩素酸イオン、４−フッ化ホウ素イオン、６−フッ化リ
ンイオン、６−フッ化タリウムイオン、６−フッ化アン
チモンイオン、チオシアンイオン、ハロゲンイオン、硫
酸イオン、硝酸イオンなどを陰イオンとし、アルカリ金
属イオン、アルカリ土類金属イオン、周期律表第３族金
属イオン、遷移金属イオン、貴金属イオン、テトラアル
キルアンモニウムイオン等を陰イオンとする一般公知の
電解質が挙げられるが、とくにその種類に限定されるも
のではない。Moreover, as the electrolyte used in the present invention, perchlorate ion, 4-boron fluoride ion, 6-phosphorus ion, 6-thallium fluoride ion, 6-antimony fluoride ion, thiocyan ion, halogen ion, sulfuric acid. Ions, nitrate ions, etc. as anions, and alkali metal ions, alkaline earth metal ions, Group 3 metal ions of the periodic table, transition metal ions, noble metal ions, tetraalkylammonium ions, etc. as anions are generally known electrolytes. However, the type is not particularly limited.
さらに、本発明に用いられる溶媒としては、プロピレ
ンカーボネート、1,2−ジメトキシエタン、４−ブチロ
ラクトン、テトラヒドロフラン、ジメチルホルムアミ
ド、アセトニトリル、ジメチルスルホキシド等、一般に
二次電池に用いられている有機溶媒を挙げることができ
る。Furthermore, examples of the solvent used in the present invention include propylene carbonate, 1,2-dimethoxyethane, 4-butyrolactone, tetrahydrofuran, dimethylformamide, acetonitrile, dimethyl sulfoxide, and the like, which are generally used organic solvents for secondary batteries. You can
以上、説明してきたように、本発明品は特殊な炭素層
面の配向構造をもつ微細な炭素繊維を正極活物質として
用いることにより、非水電解質二次電池の充放電電気量
の格段の向上を可能としたものであり、極めて利用価値
の高いものである。As described above, the product of the present invention uses the fine carbon fiber having the special orientation structure of the carbon layer surface as the positive electrode active material, thereby significantly improving the charge / discharge electricity amount of the non-aqueous electrolyte secondary battery. It has been made possible and has extremely high utility value.
以下、実施例に基づいて本発明をさらに詳しく説明す
るが、もちろん、これらの実施例に限定されるものでは
ない。Hereinafter, the present invention will be described in more detail based on examples, but of course the present invention is not limited to these examples.
実施例１ 2500℃で熱処理した図１のような炭素繊維軸に対する
炭素層面の特殊な配向構造をもつ黒鉛質炭素繊維0.1gを
チタン網に包んだものを正極、金属リチウム0.1gをニッ
ケル網に圧着したものを負極、および濃度1mol/lの過塩
素酸リチウムのプロピレンカーボネート溶液を電解液と
して二次電池を構成し、これに電流20mAで炭素1g当り36
0クーロンの電気量を充電し、ついで5.1kΩの負荷抵抗
を用いて充電させたところ、図２のような充放電曲線５
が得られた。このとき、放電電気量は炭素1g当り160ク
ーロン、アンペア時効率は44.4％であった。また、放電
中の電池電圧は5Vから3Vまで低下したが、平均電池電圧
を4Vとして求めたエネルギー密度は炭素1kg当り178Whで
あった。Example 1 0.1 g of graphitic carbon fibers having a special orientation structure of the carbon layer surface with respect to the carbon fiber axis heat-treated at 2500 ° C. as shown in FIG. 1 was wrapped in a titanium mesh, and 0.1 g of metallic lithium was used as a nickel mesh. A secondary battery was constructed by using the pressure-bonded product as a negative electrode and a propylene carbonate solution of lithium perchlorate having a concentration of 1 mol / l as an electrolytic solution.
When the electric charge of 0 coulomb was charged and then the load resistance of 5.1 kΩ was used, the charging / discharging curve 5 as shown in Fig. 2 was obtained.
was gotten. At this time, the discharged electricity amount was 160 coulombs per 1 g of carbon, and the ampere-hour efficiency was 44.4%. The battery voltage during discharge dropped from 5V to 3V, but the energy density determined with the average battery voltage of 4V was 178Wh / kg of carbon.
実施例２ 実施例１と同じ二次電池に20mAの電流で炭素1g当り14
40クーロンの電気量を充電し、2kΩの負荷抵抗を用いて
放電させたところ炭素1g当り374クーロンの放電電気量
となった。アンペア時効率は26％、平均電池電圧は4V、
エネルギー密度は炭素1kg当り416Whであった。充放電の
サイクル寿命は250回以上であった。Example 2 The same secondary battery as in Example 1 was used.
When charged with 40 coulombs of electricity and discharged using a load resistance of 2 kΩ, the amount of electricity discharged was 374 coulombs per 1 g of carbon. Ampere hour efficiency is 26%, average battery voltage is 4V,
The energy density was 416 Wh / kg carbon. The charge / discharge cycle life was 250 times or more.
実施例３ 2500℃で熱処理した図１のような炭素繊維軸に対する
炭素層面の特殊な配向構造をもつ黒鉛質炭素繊維0.1gを
チタン網に包んだものを正極、金属リチウムをニッケル
網に圧着したものを負極、および濃度1mol/lの４−フッ
化ホウ素リチウムのプロピレンカーボネート溶液を電解
溶液として二次電池を構成し、これに電流5mAで炭素1g
当り360クーロンの電気量を充電し、ついで5.1kΩの負
荷抵抗を用いて充電させたところ、炭素1g当り144クー
ロンの放電電気量となった。アンペア時効率は40％、ま
たは平均電池電圧は4V、エネルギー密度は炭素1kg当り1
60Whであった。Example 3 0.1 g of graphitic carbon fiber having a special orientation structure of the carbon layer surface with respect to the carbon fiber axis heat-treated at 2500 ° C. as shown in FIG. A secondary battery was constructed by using the negative electrode as the negative electrode and a propylene carbonate solution of lithium 4-boron fluoride having a concentration of 1 mol / l as an electrolytic solution.
When charged with 360 coulombs of electricity per charge and then with a load resistance of 5.1 kΩ, the discharge electricity of 144 coulombs per gram of carbon was obtained. Efficiency is 40% per ampere, or average battery voltage is 4V, energy density is 1 per kg of carbon
It was 60Wh.
実施例４ 実施例３と同じ電池に10mAの電池で炭素1g当り720ク
ーロンの電気量を充電し、5.1kΩの負荷抵抗を用いて放
電させたところ、炭素1g当り200クーロンの放電電気量
となった。アンペア時効率は28％、平均電池電圧は4V、
エネルギー密度は炭素1kg当り222Whであった。充放電の
サイクル寿命は250回以上であった。Example 4 The same battery as in Example 3 was charged with a 10 mA battery at an electric charge of 720 coulombs per 1 g of carbon and discharged using a load resistance of 5.1 kΩ, resulting in an electric discharge amount of 200 coulombs per 1 g of carbon. It was Ampere hour efficiency is 28%, average battery voltage is 4V,
The energy density was 222 Wh / kg carbon. The charge / discharge cycle life was 250 times or more.
比較例１ 比重1.56〜1.57g/cm3の日本カーボン（株）製の熱分
解黒鉛0.6gを正極として実施例１と同様の二次電池を作
り、これに10mAの電流で炭素1g当り220クーロンの電気
量を充電し、5.1kΩの負荷抵抗を用いて放電させたとこ
ろ、炭素1g当りの放電電気量は79クーロンであった。Comparative Example 1 A secondary battery similar to that of Example 1 was prepared by using 0.6 g of pyrolytic graphite manufactured by Nippon Carbon Co., Ltd. having a specific gravity of 1.56 to 1.57 g / cm 3 as a positive electrode, and 220 coulombs per 1 g of carbon at a current of 10 mA. Was charged and discharged using a load resistance of 5.1 kΩ, the discharged quantity of electricity per 1 g of carbon was 79 coulombs.
第１図は炭素層面が繊維軸に対してある角度で配向した
黒鉛質炭素繊維の一例についての説明のための縦断面図
である。 第２図は本発明の実施例１における充電および放電特性
を示した図である。FIG. 1 is a longitudinal sectional view for explaining an example of a graphitic carbon fiber in which the carbon layer surface is oriented at an angle with respect to the fiber axis. FIG. 2 is a diagram showing charge and discharge characteristics in Example 1 of the present invention.
Claims (2)
て設けられている非水電解質二次電池において、炭素繊
維軸に対してその炭素層面が２ないし45度の傾斜角度で
配向して、中空構造に形成され、かつ0.1ないし３μｍ
の繊維径を有する炭素繊維が正極活物質として使用され
ていることを特徴とする非水電解質二次電池。1. In a non-aqueous electrolyte secondary battery in which an electrode is provided in contact with an organic solvent in which an electrolyte is dissolved, the carbon layer surface is oriented at an inclination angle of 2 to 45 degrees with respect to the carbon fiber axis. , Hollow structure, and 0.1 to 3 μm
A non-aqueous electrolyte secondary battery in which carbon fiber having the above fiber diameter is used as a positive electrode active material.
て設けられている非水電解質二次電池において、炭素繊
維軸に対してその炭素層面が２ないし45度の傾斜角度で
配向して、中空構造に形成され、かつ0.1ないし３μｍ
の繊維径を有する炭素繊維が正極活物質として使用され
ている二次電池において、炭素繊維軸に対する炭素層面
が、円錐状又は角錐状に形成されていることを特徴とす
る非水電解質二次電池。2. In a non-aqueous electrolyte secondary battery in which an electrode is provided in contact with an organic solvent in which an electrolyte is dissolved, the carbon layer surface is oriented at an inclination angle of 2 to 45 degrees with respect to the carbon fiber axis. , Hollow structure, and 0.1 to 3 μm
In a secondary battery in which carbon fibers having a fiber diameter of 4 are used as a positive electrode active material, the carbon layer surface with respect to the carbon fiber axis is formed in a conical shape or a pyramidal shape. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61007754A JP2516741B2 (en) | 1986-01-17 | 1986-01-17 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61007754A JP2516741B2 (en) | 1986-01-17 | 1986-01-17 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62165857A JPS62165857A (en) | 1987-07-22 |
| JP2516741B2 true JP2516741B2 (en) | 1996-07-24 |
Family
ID=11674479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61007754A Expired - Fee Related JP2516741B2 (en) | 1986-01-17 | 1986-01-17 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2516741B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2703759B2 (en) * | 1986-08-28 | 1998-01-26 | 日機装株式会社 | Graphite fiber / lithium rechargeable battery |
| JPH0821375B2 (en) * | 1990-06-28 | 1996-03-04 | 新日本製鐵株式会社 | Negative electrode for lithium secondary battery |
| JP3556270B2 (en) * | 1994-06-15 | 2004-08-18 | 株式会社東芝 | Lithium secondary battery |
| US10411291B2 (en) * | 2017-03-22 | 2019-09-10 | Nanotek Instruments, Inc. | Multivalent metal ion battery having a cathode layer of protected graphitic carbon and manufacturing method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036315A (en) * | 1983-08-10 | 1985-02-25 | Toray Ind Inc | Carbon fiber structure and secondary battery using it |
-
1986
- 1986-01-17 JP JP61007754A patent/JP2516741B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036315A (en) * | 1983-08-10 | 1985-02-25 | Toray Ind Inc | Carbon fiber structure and secondary battery using it |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62165857A (en) | 1987-07-22 |
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