JP2854095B2 - Non-aqueous secondary battery - Google Patents
Non-aqueous secondary batteryInfo
- Publication number
- JP2854095B2 JP2854095B2 JP2160875A JP16087590A JP2854095B2 JP 2854095 B2 JP2854095 B2 JP 2854095B2 JP 2160875 A JP2160875 A JP 2160875A JP 16087590 A JP16087590 A JP 16087590A JP 2854095 B2 JP2854095 B2 JP 2854095B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- battery
- layer
- secondary battery
- thin
- 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
- 229920001940 conductive polymer Polymers 0.000 claims description 8
- 229920000767 polyaniline Polymers 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229920000128 polypyrrole Polymers 0.000 description 6
- 239000010409 thin film Substances 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は、導電性ポリマーを電極材料に用いる非水系
二次電池に関するものである。The present invention relates to a nonaqueous secondary battery using a conductive polymer as an electrode material.
（ロ） 従来の技術 例えば特開昭56−136469号公報に開示されているよう
に、ポリピロール、ポリアセチレン、ポリチオフェンな
どの導電性ポリマーを電極材料とする非水系二次電池は
軽量で高エネルギー密度を有し、且つ無公害であるため
近年において特に注目されている。(B) Conventional technology As disclosed in, for example, JP-A-56-136469, a non-aqueous secondary battery using a conductive polymer such as polypyrrole, polyacetylene, or polythiophene as an electrode material has a light weight and a high energy density. In recent years, it has attracted special attention because it has no pollution.
ところが非水系電解質を用いる関係上、大電流を取出
せないという致命的な問題があった。However, there is a fatal problem that a large current cannot be obtained due to the use of a non-aqueous electrolyte.
これに対して本発明は、特開昭62−246270号公報に開
示された如く、セパレータ部材の一方の面に正極として
の導電性ポリマー薄層を形成すると共に、他方の面に負
極としての導電性ポリマー薄層あるいはアルカリ金属薄
層を形成し、且つこれら正負極の各表面に集電層を形設
したる電極体を備えた構造の非水系二次電池を提案し
た。これは、電極間距離を小さくして内部抵抗を減少さ
せ、大電流の取出しを可能ならしめようとするものであ
る。On the other hand, according to the present invention, as disclosed in JP-A-62-246270, a conductive polymer thin layer as a positive electrode is formed on one surface of a separator member, and a conductive polymer layer as a negative electrode is formed on the other surface. A non-aqueous secondary battery having a structure in which a thin conductive polymer layer or a thin alkali metal layer is formed and an electrode body having a current collecting layer formed on each surface of the positive and negative electrodes has been proposed. This is intended to reduce the distance between the electrodes, reduce the internal resistance, and enable the extraction of a large current.
しかし、このタイプの二次電池は電極厚みが大きくな
ると電極に外力が加わった時に電極材料にクラックが発
生しやすく、そのために電池容量が減少するという欠点
を有している。また、導電性ポリマーとしてポリピロー
ルを用いていたが、ポリピロールは粒状のためこの欠点
を更に助長する可能性が高かった。However, this type of secondary battery has the disadvantage that when the electrode thickness is increased, cracks are likely to occur in the electrode material when an external force is applied to the electrode, thereby reducing the battery capacity. Although polypyrrole was used as the conductive polymer, polypyrrole was more likely to further promote this disadvantage due to its granular nature.
（ハ） 発明が解決しようとする課題 本発明は前記問題点に鑑みてなされたものであって、
電極に外力が加わった場合に生じる電極材料のクラック
発生の防止、またクラックによる電池容量の低下を抑制
しようとするものである。(C) Problems to be solved by the invention The present invention has been made in view of the above problems,
An object of the present invention is to prevent the occurrence of cracks in the electrode material when an external force is applied to the electrodes, and to suppress a decrease in battery capacity due to the cracks.
（ニ） 課題を解決するための手段 本発明は、セパレータ部材の一方の面に正極としての
ポリアニリン薄層を形成すると共に、他方の面に負極と
しての導電性ポリマー薄層あるいはアルカリ金属薄層を
形成し、且つこれら正、負極の各表面に集電層を形設し
た電極体を備えた非水系二次電池であって、前記ポリア
ニリン薄層の厚みが200μｍ以下であることを特徴とす
るものである。(D) Means for Solving the Problems According to the present invention, a polyaniline thin layer as a positive electrode is formed on one surface of a separator member, and a conductive polymer thin layer or an alkali metal thin layer as a negative electrode is formed on the other surface. A non-aqueous secondary battery formed and provided with an electrode body having a current collecting layer formed on each surface of the positive and negative electrodes, wherein the thickness of the polyaniline thin layer is 200 μm or less. It is.
（ホ） 作用 従来の粒状のポリピロールでなく、フィブリル状の
ポリアニリンを用いることで、電極にある程度のフレキ
シブル性が生じ、外力が加わっても容易にクラックが生
じない。(E) Action By using fibril-shaped polyaniline instead of conventional granular polypyrrole, the electrode has a certain degree of flexibility and does not easily crack even when an external force is applied.
電極材料厚みを200μｍ以下にすることによって、
電極表面と内部の外力による歪みの差を小さくすること
ができ、電極強度が向上する。By reducing the electrode material thickness to 200 μm or less,
The difference in distortion due to external force between the electrode surface and the inside can be reduced, and the electrode strength is improved.
上記、の理由により、電極からの電極材料の脱落
が防止でき、電池容量の劣化を防止できる。For the above-mentioned reasons, it is possible to prevent the electrode material from falling off from the electrode and prevent the battery capacity from deteriorating.
また、本発明の構造によれば、正負極、セパレータ間
の密着性が向上し、内部抵抗が減じられる。又、電池体
積を小さくでき電池の薄型化、小型化が計れる。Further, according to the structure of the present invention, the adhesion between the positive and negative electrodes and the separator is improved, and the internal resistance is reduced. Also, the battery volume can be reduced, and the battery can be made thinner and smaller.
尚、セパレータ部材としては合成樹脂製の微孔性薄膜
或いは不織布などを用いることができるが、微孔性薄膜
の場合にはより薄型化が可能となる利点がある。As the separator member, a microporous thin film made of synthetic resin or a nonwoven fabric can be used. However, a microporous thin film has an advantage that it can be made thinner.
（へ） 実施例 ポリプロピレン製微孔性薄膜をセパレータとし、この
セパレータの一方の面に正極としてのポラアニリン薄層
をプラズマ重合法により形成する。プラズマ重合は、チ
ャンバー内圧力0.5torr、6.5KHzの低周波電源によりプ
ラズマ重合電流50mAで行なった。その後、セパレータの
他方の面に負極としてのリチウム金属薄層を蒸着により
形成した。蒸着は真空蒸着により５分間行なった。(F) Example A polypropylene microporous thin film was used as a separator, and a polaraniline thin layer as a positive electrode was formed on one surface of the separator by a plasma polymerization method. The plasma polymerization was performed at a plasma polymerization current of 50 mA using a low-frequency power supply of 6.5 KHz and a chamber pressure of 0.5 torr. Thereafter, a lithium metal thin layer as a negative electrode was formed on the other surface of the separator by vapor deposition. The evaporation was performed for 5 minutes by vacuum evaporation.
ここで、ポリアリニン薄層（電極材料）の厚みはプラ
ズマ重合時間を調節することにより制御し、それぞれ厚
み10μｍ、100μｍ、150μｍ、180μｍ、200μｍ、240
μｍのものを作製した。これらをそれぞれ後述する電池
Ａ、Ｂ、Ｃ、Ｄ、Ｅ、Ｘに用いた。Here, the thickness of the polyarynin thin layer (electrode material) is controlled by adjusting the plasma polymerization time, and the thickness is 10 μm, 100 μm, 150 μm, 180 μm, 200 μm, 240 μm, respectively.
μm was prepared. These were used for batteries A, B, C, D, E, and X described below, respectively.
ついで正、負極の各表面にステンレスをスパッタリン
グして集電層を形成した。尚、スパッタリング条件はチ
ャンバー内のアルゴンガス圧７×10-3Torr.においてス
パッタリング電流100mAで10分間行なった。Next, stainless steel was sputtered on each surface of the positive and negative electrodes to form a current collecting layer. The sputtering was performed for 10 minutes at a sputtering current of 100 mA at an argon gas pressure of 7 × 10 −3 Torr in the chamber.
以上のようにして形成した厚さ0.12mm、幅12mm、長さ
200mmの電極体の両面に幅12mm、長さ220mmのポリプロピ
レン製微孔性薄膜を重ね渦巻状に巻取った後、電池罐に
封入し、電解液としてプロピレンカーボネートに過塩素
酸リチウムを２モル／溶解したものを用いて、本発明
電池Ａ、Ｂ、Ｃ、Ｄ、Ｅ比較電池Ｘを作製した。Thickness 0.12mm, width 12mm, length formed as above
A microporous thin film made of polypropylene having a width of 12 mm and a length of 220 mm is laminated on both sides of a 200 mm electrode body, wound up in a spiral shape, and then sealed in a battery can. As an electrolyte, propylene carbonate is mixed with 2 mol / l of lithium perchlorate. Batteries A, B, C, D and E Comparative batteries X were prepared from the dissolved batteries.
尚、上記実施例では、ポリアニリン薄層の形成法とし
てプラズマ重合法の場合を例示したが、その他に気相化
学重合法も適用しうる。気相化学重合法としてはセパレ
ータの一方の面に酸化剤である過塩素酸鉄を例えば水な
どの溶媒に溶解したものを塗布し、アニリン蒸気中に保
持させることによりポリアリニン薄層が形成される。In the above embodiment, the plasma polymerization method is exemplified as a method for forming the polyaniline thin layer. However, a gas phase chemical polymerization method may be applied. As a gas-phase chemical polymerization method, a thin layer of polyarynin is formed by applying a solution of iron perchlorate, which is an oxidizing agent, in a solvent such as water on one surface of a separator and holding the solution in aniline vapor. .
更に比較電池として、同様なプラズマ重合法で形成し
たポリピロール薄層（厚み100μｍ）を用いた以外は上
記と同様にして、比較電池Ｙを作製した。Further, as a comparative battery, a comparative battery Y was produced in the same manner as described above except that a polypyrrole thin layer (100 μm in thickness) formed by the same plasma polymerization method was used.
これらの電池を用い、電池の充放電特性を比較した。
この時の充放電条件は、電流0.4Aで１分間充電し、電流
0.4Aで電池電圧が2.5Vに達するまで放電するというもの
である。Using these batteries, the charge and discharge characteristics of the batteries were compared.
The charge and discharge conditions at this time are as follows: charge at a current of 0.4 A for 1 minute,
It discharges at 0.4A until the battery voltage reaches 2.5V.
第１図は、これらの電池の放電容量比較図である。第
１図より、本発明電池Ａ、Ｂ、Ｃ、Ｄ、Ｅは、比較電池
Ｘ、Ｙに比べて、大きな放電容量を示すことが理解でき
る。ここで、電極材料厚みが200μｍを越える（比較電
池Ｘ）と、放電容量が低下することがわかる。これは、
電極材料厚みが200μｍを越えると、外力によってクラ
ックが入りやすくなるためである。FIG. 1 is a comparison diagram of the discharge capacities of these batteries. From FIG. 1, it can be understood that the batteries A, B, C, D, and E of the present invention show a larger discharge capacity than the comparative batteries X and Y. Here, it can be seen that when the electrode material thickness exceeds 200 μm (Comparative Battery X), the discharge capacity decreases. this is,
If the thickness of the electrode material exceeds 200 μm, cracks are likely to occur due to external force.
また本発明電池Ｂと比較電池Ｙは、電極厚みが同じで
あるが、電極材料であるフィブリル状のポリアニリン
（Ｂ）と、粒状のポリピロール（Ｙ）の電極強度の差が
反映され、電池Ｂの放電容量が大きくなっている。The battery B of the present invention and the comparative battery Y have the same electrode thickness, but reflect the difference in electrode strength between the fibril-shaped polyaniline (B), which is an electrode material, and the granular polypyrrole (Y). The discharge capacity has increased.
尚、薄層を形成するに際して実施例で示したプラズマ
重合法を用いれば、電極表面が粗面化され表面積が増大
して活物質の利用率が向上し更に放電容量の増大が計れ
るという利点がある。In addition, when the plasma polymerization method described in the embodiment is used to form a thin layer, there is an advantage that the electrode surface is roughened, the surface area is increased, the utilization rate of the active material is improved, and the discharge capacity can be further increased. is there.
（ト） 発明の効果 上述した如く、本発明によれば、ポリアニリン薄層厚
みを200μｍ以下としているので、電池の充放電特性を
改善しうると共に、更にこの種電池の薄型化、小型化が
計れるものであり、その工業的価値は極めて大である。(G) Effect of the Invention As described above, according to the present invention, the polyaniline thin layer has a thickness of 200 μm or less, so that the charge / discharge characteristics of the battery can be improved, and furthermore, this type of battery can be made thinner and smaller. And its industrial value is extremely large.
第１図は、本発明電池と比較電池との放電容量比較図で
ある。 Ａ、Ｂ、Ｃ、Ｄ、Ｅ……本発明電池、 Ｘ、Ｙ……比較電池。FIG. 1 is a comparison diagram of the discharge capacity between the battery of the present invention and a comparative battery. A, B, C, D, E: battery of the present invention, X, Y: comparative battery.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 10/36 - 10/40 H01M 4/36 - 4/62──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 10/36-10/40 H01M 4/36-4/62
Claims (1)
ポリアニリン薄層を形成すると共に、他方の面に負極と
しての導電性ポリマー薄層あるいはアルカリ金属薄層を
形成し、且つこれら正、負極の各表面に集電層を形設し
た電極体を備えた電池であって、 前記ポリアニリン薄層の厚みが200μｍ以下であること
を特徴とする非水系二次電池。A thin polyaniline layer as a positive electrode is formed on one surface of a separator member, and a thin conductive polymer layer or a thin alkali metal layer as a negative electrode is formed on the other surface. A non-aqueous secondary battery, comprising: an electrode body having a current collecting layer formed on each surface, wherein the thickness of the polyaniline thin layer is 200 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2160875A JP2854095B2 (en) | 1990-06-19 | 1990-06-19 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2160875A JP2854095B2 (en) | 1990-06-19 | 1990-06-19 | Non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0451474A JPH0451474A (en) | 1992-02-19 |
| JP2854095B2 true JP2854095B2 (en) | 1999-02-03 |
Family
ID=15724262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2160875A Expired - Fee Related JP2854095B2 (en) | 1990-06-19 | 1990-06-19 | Non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2854095B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100553025C (en) | 2005-01-26 | 2009-10-21 | 松下电器产业株式会社 | Negative electrode for lithium secondary battery, lithium secondary battery using the same, and their manufacturing method |
-
1990
- 1990-06-19 JP JP2160875A patent/JP2854095B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0451474A (en) | 1992-02-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |