JP3144929B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3144929B2 JP3144929B2 JP32765492A JP32765492A JP3144929B2 JP 3144929 B2 JP3144929 B2 JP 3144929B2 JP 32765492 A JP32765492 A JP 32765492A JP 32765492 A JP32765492 A JP 32765492A JP 3144929 B2 JP3144929 B2 JP 3144929B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- electrolyte secondary
- secondary battery
- aqueous electrolyte
- positive electrode
- 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
-
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は充放電可能な正極を備え
た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 having a chargeable / dischargeable positive electrode.
【０００２】[0002]
【従来の技術】これまでに、ポリアニリン、ポリアセ
ン、ポリアセチレン、ポリピロール、ポリチオフェンな
どの導電性高分子ならびに炭素材料は、酸化還元挙動を
有することから、電池電極材料として注目をあつめてき
た。これら電極材料は、軽量かつ可とう性に優れ、特に
負極に金属リチウムを用いた場合、高電圧、高エネルギ
ー密度の電池となりうることが知られている。これら材
料を正極に用いた場合、充電時に電解液中のアニオンを
取り込み、逆に放電時にアニオンを放出する。単位重量
当りの電気量で示すと、最高２００ｍＡｈ／ｇに達する
材料も存在する。特にポリアニリンを正極とした電池は
商品化されている。2. Description of the Related Art Heretofore, conductive polymers such as polyaniline, polyacene, polyacetylene, polypyrrole, and polythiophene and carbon materials have attracted attention as battery electrode materials because of their redox behavior. It is known that these electrode materials are lightweight and excellent in flexibility, and in particular, when metal lithium is used for the negative electrode, it can be a high voltage and high energy density battery. When these materials are used for the positive electrode, they take in anions in the electrolyte during charging and release the anions during discharging. Some materials can reach up to 200 mAh / g in terms of electricity per unit weight. In particular, batteries using polyaniline as a positive electrode have been commercialized.
【０００３】[0003]
【発明が解決しようとする課題】しかし、これらの材料
だけで非水電解液二次電池は構成されるのではなく、電
解液などその他の材料を考慮すると、必ずしも高エネル
ギー密度ではなくなる。またこれら材料の比重の低いこ
とは、逆に体積当りのエネルギー密度を大幅に低下させ
ることになる。またサイクル寿命を考慮した場合、理論
容量よりもかなり低い部分で充放電する必要があった。
このため高エネルギー密度の非水電解液二次電池を得る
ためにはさらに高容量な正極が必要となる。本発明は前
記従来の問題に留意し、高エネルギー密度で、かつ保存
性のよい非水電解液二次電池を提供することを目的とす
る。However, a non-aqueous electrolyte secondary battery is not constituted only by these materials, but does not necessarily have a high energy density in consideration of other materials such as an electrolyte. On the other hand, the low specific gravity of these materials significantly reduces the energy density per volume. In addition, in consideration of the cycle life, it was necessary to charge and discharge a portion considerably lower than the theoretical capacity.
Therefore, in order to obtain a non-aqueous electrolyte secondary battery having a high energy density, a positive electrode having a higher capacity is required. SUMMARY OF THE INVENTION An object of the present invention is to provide a non-aqueous electrolyte secondary battery having a high energy density and good storage stability, while keeping in mind the above conventional problems.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記目的を達
成するために、充放電可能な正極と、非水電解液と、充
放電可能な負極を具備する非水電解液二次電池であっ
て、その正極にＣ5 Ｎを用いる構成とする。In order to achieve the above object, the present invention provides a non-aqueous electrolyte secondary battery having a chargeable / dischargeable positive electrode, a nonaqueous electrolyte, and a chargeable / dischargeable negative electrode. Thus, a configuration is used in which C 5 N is used for the positive electrode.
【０００５】[0005]
【作用】Ｃ5 Ｎを構成する窒素（Ｎ）は２Ｓ軌道に２
個、２Ｐ軌道に３個の電子を持ち、炭素は２Ｓ軌道に２
個、２Ｐ軌道に２個の電子を持つ。したがって炭素に比
べて電子が１個過剰な状態になる。[Function] Nitrogen (N) constituting C 5 N is 2S orbital.
Has 2 electrons in the 2S orbit and 3 electrons in the 2P orbit.
Each has 2 electrons in 2P orbitals. Therefore, there is one more electron than carbon.
【０００６】このような電子状態であるため、ゲスト物
質をインターカレーションさせなくても、Ｃ5 Ｎが高い
電気伝導性を有する理由と考えられる。ここでＣ5 Ｎ正
極を非水電解液中で充電すると、導電性高分子ならびに
炭素材料同様に、正極中にアニオンが吸蔵され、放電す
ると吸蔵されたアニオンが電解液中に放出される。また
そのときの平均放電電圧は、Ｌｉ極に対して４．５Ｖで
放電容量も１６０ｍＡｈ／ｇであった。このように正極
にＣ5 Ｎを用いることで、高容量で高電圧な非水電解液
二次電池とすることができる。Because of such an electronic state, it is considered that C 5 N has high electric conductivity without intercalating the guest substance. Here, when the C 5 N positive electrode is charged in the non-aqueous electrolyte, the anion is occluded in the positive electrode, similarly to the conductive polymer and the carbon material, and the discharged anion is released into the electrolyte when discharged. The average discharge voltage at that time was 4.5 V with respect to the Li electrode, and the discharge capacity was 160 mAh / g. Thus, by using the C 5 N to the positive electrode can be a high voltage nonaqueous electrolyte secondary battery with high capacity.
【０００７】[0007]
【実施例】以下本発明の実施例を詳細に説明する。 （実施例１）Ｃ5 Ｎの電極としての特性を検討するた
め、図１に示すコイン型の非水電解液二次電池を作っ
た。Embodiments of the present invention will be described below in detail. Example 1 A coin-type non-aqueous electrolyte secondary battery shown in FIG. 1 was manufactured in order to examine the characteristics of C 5 N as an electrode.
【０００８】Ｃ5 Ｎ１０ｇに対して結着剤としてポリ４
フッ化エチレン１ｇを混合して合剤とした。この合剤
０．１ｇを直径１７．５ｍｍに加圧成型してＣ5 Ｎ電極
１とし、ケース２の中に置いた。微孔性ポリプロピレン
セパレータ３をＣ5 Ｎ電極１上に置いた。１モル／１の
過塩素酸リチウム（ＬｉＣｌＯ4 ）を溶解したプロピレ
ンカーボネート（ＰＣ）を非水電解質としてセパレータ
３上に注液した。この上に、内側に直径１７．５ｍｍの
金属Ｌｉ４を張り付け、外周部にポリプロピレンガスケ
ット５を付けた封口板６を置いて封口し、コイン型非水
電解液二次電池を作製した。Poly 4 is used as a binder for 10 g of C 5 N.
1 g of fluorinated ethylene was mixed to prepare a mixture. 0.1 g of this mixture was pressure-molded to a diameter of 17.5 mm to form a C 5 N electrode 1, which was placed in a case 2. The microporous polypropylene separator 3 was placed on the C 5 N electrode 1. Propylene carbonate (PC) in which 1 mol / 1 of lithium perchlorate (LiClO 4 ) was dissolved was poured on the separator 3 as a non-aqueous electrolyte. On top of this, metal Li4 having a diameter of 17.5 mm was adhered on the inside, and a sealing plate 6 with a polypropylene gasket 5 attached on the outer periphery was placed and sealed to produce a coin-type nonaqueous electrolyte secondary battery.
【０００９】そして２ｍＡの定電流で、Ｃ5 Ｎ電極１が
Ｌｉ対極４に対して４．７Ｖになるまでアノード分極
（Ｃ5 Ｎ電極を正極として見る場合には充電に相当）
し、次にＣ5 Ｎ電極１が３．０Ｖになるまでカソード分
極（放電に相当）した。そしてこのアノード分極、カソ
ード分極を繰り返し行なった。Then, at a constant current of 2 mA, the anode is polarized until the C 5 N electrode 1 becomes 4.7 V with respect to the Li counter electrode 4 (corresponding to charging when the C 5 N electrode is viewed as a positive electrode).
Then, the cathode was polarized (corresponding to discharge) until the C 5 N electrode 1 reached 3.0 V. The anodic polarization and the cathodic polarization were repeated.
【００１０】従来例として、気相成長法炭素材料ならび
にポリアニリンを用いて、Ｃ5 Ｎ電極と同様に電極を作
製し、次に同じように試験セルを作りアノード分極、カ
ソード分極を繰り返し行なった。以後気相成長法炭素材
料ならびにポリアニリンを用いた電極をＣ電極、Ｐ電極
と略す。なおＰ電極に関しては、Ｌｉ対極に対して４．
０Ｖになるまでアノード分極（正極として見る場合には
充電に相当）し、次にＰ電極が３．０Ｖになるまでカソ
ード分極（放電に相当）した。そしてこのアノード分
極、カソード分極を繰り返し行なった。As a conventional example, an electrode was produced in the same manner as a C 5 N electrode using a carbon material grown by vapor deposition and polyaniline, and then a test cell was produced in the same manner, and anodic polarization and cathodic polarization were repeatedly performed. Hereinafter, electrodes using the vapor-grown carbon material and polyaniline are abbreviated as C electrode and P electrode. As for the P electrode, 4. with respect to the Li counter electrode.
Anode polarization (corresponding to charging when viewed as a positive electrode) was performed until the voltage reached 0 V, and then cathodic polarization (corresponding to discharge) was performed until the P electrode reached 3.0 V. The anodic polarization and the cathodic polarization were repeated.
【００１１】Ｃ5 Ｎ電極、Ｃ電極、Ｐ電極の１サイクル
目の充放電曲線を図２に示す。また（表１）に初期放電
容量、初期放電容量に対する１００サイクル目の非水電
解液二次電池の放電容量の容量維持率を示す。FIG. 2 shows the charge / discharge curves of the C 5 N electrode, C electrode and P electrode in the first cycle. Table 1 shows the initial discharge capacity and the capacity retention ratio of the discharge capacity of the nonaqueous electrolyte secondary battery at the 100th cycle with respect to the initial discharge capacity.
【００１２】[0012]
【表１】 [Table 1]
【００１３】前記図２および（表１）より明らかなよう
に、放電電圧はＣ5 Ｎ電極が、Ｃ電極ならびにＰ電極よ
り高く、また電気容量もＣ5 Ｎ電極が１６０ｍＡｈ／ｇ
と大きいことがわかった。また１００サイクル目の放電
容量維持率もＣ5 Ｎが最も高い値を示した。 （実施例２）本実施例では、高温保存特性について調べ
た。As apparent from FIG. 2 and Table 1, the discharge voltage of the C 5 N electrode is higher than that of the C and P electrodes, and the discharge capacity of the C 5 N electrode is 160 mAh / g.
It turned out to be big. The 100 th cycle discharge capacity retention ratio was the highest value C 5 N. Example 2 In this example, high-temperature storage characteristics were examined.
【００１４】Ｃ5 Ｎを正極とする図１に示すコイン型の
非電解液二次電池を構成した。また従来例として、気相
成長法炭素材料ならびにポリアニリンを用いて、Ｃ5 Ｎ
電極と同様にＣ電極、Ｐ電極を正極としたコイン型の非
水電解液二次電池を作製した。この非水電解液二次電池
の作製法は実施例１と同様の方法で行った。A coin-type non-electrolyte secondary battery shown in FIG. 1 was constructed using C 5 N as a positive electrode. Further, as a conventional example, C 5 N is formed using a vapor-grown carbon material and polyaniline.
A coin-type non-aqueous electrolyte secondary battery having a C electrode and a P electrode as positive electrodes was prepared in the same manner as the electrodes. This non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 1.
【００１５】非水電解液二次電池の高温保存試験は、次
の方法で行った。２０℃、２ｍＡの定電流でＣ5 Ｎ電
極、Ｃ電極に関しては、４．７Ｖまで、Ｐ電極に関して
は、４．０Ｖまで充電し、次にいずれの非水電解液二次
電池も３．０Ｖまで放電し、この充放電を５サイクル行
い、６サイクル目の充電が終わった後、６０℃で３週間
保存した。保存後２０℃に戻して、同条件で放電した。
ここで容量維持率は次のように定義した。The high-temperature storage test of the non-aqueous electrolyte secondary battery was performed by the following method. At 20 ° C. and 2 mA constant current, the C 5 N electrode and the C electrode were charged up to 4.7 V, and the P electrode was charged up to 4.0 V. Then, any of the nonaqueous electrolyte secondary batteries was charged at 3.0 V. The battery was stored at 60 ° C. for 3 weeks after charging and discharging were performed for 5 cycles, and after charging at the 6th cycle was completed. After storage, the temperature was returned to 20 ° C., and the battery was discharged under the same conditions.
Here, the capacity retention rate was defined as follows.
【００１６】容量維持率＝１００×６サイクル目の放電
容量／５サイクル目の放電容量 また保存終了後に充電を行い、その後の放電容量を評価
した。ここで容量回復率を次のように定義した。Capacity retention ratio = 100 × discharge capacity at 6th cycle / 5th discharge capacity At the end of storage, charging was performed, and the subsequent discharge capacity was evaluated. Here, the capacity recovery rate was defined as follows.
【００１７】容量回復率＝１００×７サイクル目の放電
容量／５サイクル目の放電容量 （表２）に各非水電解液二次電池の３週間後の容量維持
率、容量回復率を示す。Capacity recovery rate = 100 × 7th cycle discharge capacity / 5th cycle discharge capacity (Table 2) shows the capacity retention rate and capacity recovery rate of each nonaqueous electrolyte secondary battery after 3 weeks.
【００１８】[0018]
【表２】 [Table 2]
【００１９】上表より明らかなようにＣ5 Ｎ電極を用い
た非水電解液二次電池が、容量維持率ならびに容量回復
率がＣ電極、Ｐ電極を用いた非水電解液二次電池に比べ
て最も大きい。As is clear from the above table, the non-aqueous electrolyte secondary battery using the C 5 N electrode is different from the non-aqueous electrolyte secondary battery using the C electrode and the P electrode in the capacity retention rate and the capacity recovery rate. The largest compared.
【００２０】このように、本発明の各実施例の非水電解
液二次電池は、Ｃ5 Ｎ正極を用いたことにより高い放電
電圧、高容量、優れた保存特性を有するものである。な
お本実施例ではコイン型の非水電解液二次電池で説明し
たが、円筒型、角型などの形状によって変わるものでは
ない。As described above, the non-aqueous electrolyte secondary batteries of the embodiments of the present invention have high discharge voltage, high capacity, and excellent storage characteristics by using the C 5 N positive electrode. In this embodiment, the coin-type non-aqueous electrolyte secondary battery has been described.
【００２１】[0021]
【発明の効果】以上述べたように、本発明は充放電可能
な正極と、非水電解液と、充放電可能な負極を具備する
非水電解液二次電池であって、前記正極にＣ5 Ｎを用い
たため、高エネルギー密度で、保存性に優れた非水電解
液二次電池を得ることができ、産業上の意義は大きい。As described above, the present invention relates to a non-aqueous electrolyte secondary battery including a chargeable / dischargeable positive electrode, a nonaqueous electrolyte, and a chargeable / dischargeable negative electrode, wherein Since 5 N is used, a non-aqueous electrolyte secondary battery having a high energy density and excellent storage stability can be obtained, which has great industrial significance.
【図１】本発明の正極を使ったコイン型非水電解液二次
電池の断面図FIG. 1 is a cross-sectional view of a coin-type non-aqueous electrolyte secondary battery using a positive electrode of the present invention.
【図２】従来例と比較した本発明の正極を用いたコイン
型非水電解液二次電池の充放電特性図FIG. 2 is a charge / discharge characteristic diagram of a coin-type non-aqueous electrolyte secondary battery using the positive electrode of the present invention as compared with a conventional example.
１ Ｃ5 Ｎ正極 ２ ケース ３ セパレータ ４ 金属Ｌｉ ５ ガスケット ６ 封口板1 C 5 N positive electrode 2 Case 3 separator 4 metal Li 5 Gasket 6 sealing plate
フロントページの続き (72)発明者 美藤 靖彦 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 豊口 吉徳 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 平５−290843（ＪＰ，Ａ) Ｊｏｈｎ Ｋｏｕｖｅｔａｋｉｓ，Ｒ ｉｃｈａｒｄ Ｂ．Ｋａｎｅｒ，Ｍａｒ ｇａｒｅｔ Ｌ．Ｓａｔｔｌｅｒ，ａｎ ｄ Ｎｅｉｌ Ｂａｒｔｌｅｔｔ，“Ａ Ｎｏｖｅｌ Ｇｒａｐｈｉｔｅ−Ｌｉ ｋｅ Ｍａｔｅｒｉａｌ ｏｆ Ｃｏｍ ｐｏｓｉｔｉｏｎ ＢＣ▲下３▼，ａｎ ｄ Ｎｉｔｒｏｇｅｎ−Ｃａｒｂｏｎ Ｇｒａｐｈａｉｔｅｓ”，Ｊ．Ｃｈｅ ｍ．Ｓｏｃ．，Ｃｈｅｍ．Ｃｏｍｍｕ ｎ．，1986，ｐ．1758. (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 H01M 4/58 Continued on the front page (72) Inventor Yasuhiko Mito 1006 Kazuma Kadoma, Osaka Pref.Matsushita Electric Industrial Co., Ltd. 56) References JP-A-5-290843 (JP, A) John Kouvetakis, Richard B. Kaner, Mar garet L .; Sattler, and Neil Bartlett, "A Novel Graphite-Like Material of Composition BC BC <3>, and Nitrogen-Carbon Graphites", J. Amer. Chem. Soc. Chem. Commun. 1986, p. 1758. (58) Field surveyed (Int. Cl. 7 , DB name) H01M 10/40 H01M 4/58
Claims (1)
放電可能な負極を具備し、前記正極をＣ5 Ｎとした非水
電解液二次電池。1. A non-aqueous electrolyte secondary battery comprising a chargeable / dischargeable positive electrode, a non-aqueous electrolyte, and a chargeable / dischargeable negative electrode, wherein the positive electrode is C 5 N.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32765492A JP3144929B2 (en) | 1992-12-08 | 1992-12-08 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32765492A JP3144929B2 (en) | 1992-12-08 | 1992-12-08 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06176795A JPH06176795A (en) | 1994-06-24 |
| JP3144929B2 true JP3144929B2 (en) | 2001-03-12 |
Family
ID=18201477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32765492A Expired - Fee Related JP3144929B2 (en) | 1992-12-08 | 1992-12-08 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3144929B2 (en) |
-
1992
- 1992-12-08 JP JP32765492A patent/JP3144929B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ｊｏｈｎ Ｋｏｕｖｅｔａｋｉｓ，Ｒｉｃｈａｒｄ Ｂ．Ｋａｎｅｒ，Ｍａｒｇａｒｅｔ Ｌ．Ｓａｔｔｌｅｒ，ａｎｄ Ｎｅｉｌ Ｂａｒｔｌｅｔｔ，"Ａ Ｎｏｖｅｌ Ｇｒａｐｈｉｔｅ−Ｌｉｋｅ Ｍａｔｅｒｉａｌ ｏｆ Ｃｏｍｐｏｓｉｔｉｏｎ ＢＣ▲下３▼，ａｎｄ Ｎｉｔｒｏｇｅｎ−Ｃａｒｂｏｎ Ｇｒａｐｈａｉｔｅｓ"，Ｊ．Ｃｈｅｍ．Ｓｏｃ．，Ｃｈｅｍ．Ｃｏｍｍｕｎ．，１９８６，ｐ．１７５８． |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06176795A (en) | 1994-06-24 |
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