JPS6237873A - Secondary cell - Google Patents
Secondary cellInfo
- Publication number
- JPS6237873A JPS6237873A JP60178285A JP17828585A JPS6237873A JP S6237873 A JPS6237873 A JP S6237873A JP 60178285 A JP60178285 A JP 60178285A JP 17828585 A JP17828585 A JP 17828585A JP S6237873 A JPS6237873 A JP S6237873A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- positive electrode
- electrode
- conductive polymer
- discharge
- 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
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001197 polyacetylene Polymers 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 230000002269 spontaneous effect Effects 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- -1 for example Polymers 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole 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
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は二次電池に関し、詳しくは、導電性ポリマー
を電極材料とした非水電解質二次電池に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a secondary battery, and more particularly to a non-aqueous electrolyte secondary battery using a conductive polymer as an electrode material.
〈従来の技術〉
近年、導電性ポリマーを電極材料とした二次電池が提案
されている。<Prior Art> In recent years, secondary batteries using conductive polymers as electrode materials have been proposed.
この種の二次電池の電極材料となる導電性ポリマーは、
通常は導電性はわずかであるが、各種のドーパントをド
ーピング、アンド−ピングすることが可能であり、ドー
ピングにより導電性が飛躍的に上昇する。そして、アニ
オンをドーピングした導電性ポリマーは正極月利として
、またカチオンをドーピングした導電性ポリマーは負極
材料として各々使用され、ドーピング及びアンド−ピン
グを電気化学的に可逆的に行なうことにより充放電可能
な電池が構成される訳である。The conductive polymer that serves as the electrode material for this type of secondary battery is
Normally, the conductivity is slight, but it is possible to dope or undope with various dopants, and doping dramatically increases the conductivity. The conductive polymer doped with anions is used as a positive electrode material, and the conductive polymer doped with cations is used as a negative electrode material, and can be charged and discharged by electrochemically reversibly doping and undoping. In other words, a battery is constructed.
この様な導電性ポリマーとしては、例えばポリアセチレ
ン、ポリチオフェン、ポリピロール、ポリパラフェニレ
ン、ポリアニリン等が従来から知られており、いずれも
半導体的性質をもっている。As such conductive polymers, for example, polyacetylene, polythiophene, polypyrrole, polyparaphenylene, polyaniline, etc. are conventionally known, and all of them have semiconducting properties.
〈発明が解決しようとする問題点〉
しかしながら、このような導電性ポリマーを一極とした
二次電池は、数百サイクルもの寿命をもつものの、充放
電容量を増加しようとすると充、電途中に充電電圧が急
上昇し充電不能となることから充放電可能な電池容量が
少な、いという欠点があり、特に充放電サイクルがすす
む、と充電電圧が急上昇する時期が早まって充電できる
容Ｍ（充電容量）が減少するから、実用上の電池性能を
満しうるサイクル寿命を差程長くできず、また自己放電
が大きい等といった問題がある。<Problems to be Solved by the Invention> However, although such secondary batteries with conductive polymer as one pole have a lifespan of several hundred cycles, when trying to increase the charge/discharge capacity, the battery stops charging or discharging. The drawback is that the chargeable capacity of the battery is small because the charging voltage suddenly increases and charging becomes impossible.In particular, as the charging/discharging cycle progresses, the charging voltage suddenly increases earlier and the chargeable capacity M (charging capacity M) decreases. ) decreases, the cycle life that satisfies practical battery performance cannot be significantly extended, and there are problems such as large self-discharge.
これらの問題の原因は電池集電面（電池集電体表面ある
いは電池端子内面）と電極表面との集電部における接触
性かあまりよくないことに因るものと考えられており、
接触性改善のために例えば特開昭５９−１１２５８４
号公報に開示されているように電極の電池集電面側に金
属膜層を設けたり、あるいは特開昭５９−１７３９６２
号公報のように集電体として鉄合金を用いることによ
り、集電部における両面の接触抵抗を減少させ、エネル
ギー密度を増大させ、もって充電容量を増加させ、また
電池サイクル寿命を増大させること等が捉案されている
が、後述する理由によって十分な効果が得られないでい
るのか現状である。The cause of these problems is thought to be that the contact between the battery current collecting surface (the battery current collector surface or the inside surface of the battery terminal) and the electrode surface is not very good at the current collecting part.
For example, Japanese Patent Application Laid-Open No. 59-112584 to improve contactability.
A metal film layer may be provided on the battery current collecting surface side of the electrode as disclosed in Japanese Patent Application Laid-Open No. 173962/1983.
By using an iron alloy as a current collector as in the publication, it is possible to reduce the contact resistance on both sides of the current collecting part, increase the energy density, thereby increasing the charging capacity, and increasing the battery cycle life. However, the current situation is that sufficient effects have not been obtained for the reasons described below.
〈問題点を解決するための手段〉
この発明の二次電池は、導電性ポリマーを少なくとも一
方の電極とする二次電池であって、電極の電池集電面と
対向する面を炭化させてなることを要旨とする
〈作 用〉
以上のように電極面を炭化させることによってその炭化
部分が集電部を兼務するようになる他、次の理由■、■
によって充放電容量増大、電池サイクル寿命向上、並び
に自己放電防止等を図ることができる。<Means for Solving the Problems> The secondary battery of the present invention is a secondary battery in which at least one electrode is made of a conductive polymer, and the surface of the electrode facing the battery current collecting surface is carbonized. <Function> By carbonizing the electrode surface as described above, the carbonized part also serves as a current collecting part, and also for the following reasons■,■
This makes it possible to increase charge/discharge capacity, improve battery cycle life, and prevent self-discharge.
■ 充放電容量増大及び電池１ノイクル寿命向上特開昭
５９−１７３９６２ 号公報にみられるように集電体と
して鉄合金を使用したり、特開昭５９−１１２５８４号
公報にみられるように金属薄膜を蒸着などによって導電
性ポリマー上へ付着させた場合のように他の物質を接触
させる方法は接触部分での接触抵抗がある程度大きくな
るのは免れない。これに対して本発明のように導電性ポ
リマーの一部を炭化し、その炭素層を集電体として使用
すれば、この炭素層と導電性ポリマーとはもともと同じ
もので両者は連続しｎいにつなかったものであるので接
触抵抗が非常に小さくなる。このため集電部での接触抵
抗による電圧損失が非常に少なく、充電時には、充電電
圧が低く抑えられ溶媒の分解等の副反応を防止でき充電
効率が上昇する。また、放電時には放電電圧が高く維持
され、放電効率も上昇する。■ Increasing charge/discharge capacity and improving battery life per cycle. As seen in JP-A No. 59-173962, an iron alloy is used as the current collector, and as shown in JP-A-59-112584, metal thin film is used as the current collector. When a conductive polymer is attached to a conductive polymer by vapor deposition or the like, a method in which another substance is brought into contact with the conductive polymer inevitably increases the contact resistance at the contact portion to some extent. On the other hand, if a part of the conductive polymer is carbonized and the carbon layer is used as a current collector as in the present invention, the carbon layer and the conductive polymer are originally the same and are continuous. Since the contact resistance is extremely low, the contact resistance is extremely low. Therefore, voltage loss due to contact resistance at the current collector is extremely small, and during charging, the charging voltage is kept low, side reactions such as decomposition of the solvent can be prevented, and charging efficiency is increased. Further, during discharge, the discharge voltage is maintained high, and the discharge efficiency is also increased.
接触抵抗が小さいため上に述べたように溶媒の分解は殆
んど生じないうえに集電体が炭素であるため、金属蒸着
膜や金属板を集電板に使用したときに生じる集電板の溶
解等も生じない。Because the contact resistance is small, as mentioned above, almost no decomposition of the solvent occurs, and since the current collector is carbon, the current collector plate that occurs when a metal evaporated film or metal plate is used as a current collector plate. No dissolution etc. will occur.
このように副反応が殆んどないため充放電のサイクルが
経過しても集電体、電解液に変化は少なくザイクル寿命
が向上する。また、これまでの他の金属板、金属蒸着膜
を接触し集電する方法では接触抵抗による電圧損失が大
きいため充電容量を増加すると充電電圧が電解液分解電
圧を超えるため、充電容量を増加できなかったが、本発
明によれば、接触抵抗が非常に小さく、その電圧損失が
非常に少ないため充電容量を増加しても、充電電圧が電
解液分解電圧を超えないため、充電容量を増加すること
が可能である。Since there are almost no side reactions in this way, there is little change in the current collector or electrolyte even after charging and discharging cycles, and the cycle life is improved. In addition, in the conventional method of collecting current by contacting other metal plates or metal vapor deposited films, there is a large voltage loss due to contact resistance. However, according to the present invention, the contact resistance is very small and the voltage loss is very small, so even if the charging capacity is increased, the charging voltage does not exceed the electrolyte decomposition voltage, so the charging capacity can be increased. Is possible.
■ 自己放電の防止
自己放電の機構は導電性ポリマー中にドープされたドー
パントによって集電面の金属が酸化されて電解液中に溶
出し結果的に導電性ポリマーからドーパントがアンド−
ピングした状態となるとい□うメカニズムで説明できる
。従って、集電部に不活性な金属を用いれば集電部にお
ける上記酸化反応が抑制されドーパントのアンド−ピン
グが抑えられて電池の自己放電は防止できる。前記した
特開昭５９−１１２５８４ 号ではこの点に注目して集
電体として金や白金などの不活性金属を用いることによ
り自己放電抑制を効果的に行なうことが開示されている
。■ Prevention of self-discharge The mechanism of self-discharge is that the metal on the current collecting surface is oxidized by the dopant doped into the conductive polymer and dissolved into the electrolyte, resulting in the dopant being removed from the conductive polymer.
The ping state can be explained by the following mechanism. Therefore, if an inert metal is used in the current collecting part, the above-mentioned oxidation reaction in the current collecting part is suppressed, dopant and-doping is suppressed, and self-discharge of the battery can be prevented. The above-mentioned Japanese Patent Laid-Open No. 59-112584 focuses on this point and discloses that self-discharge can be effectively suppressed by using an inert metal such as gold or platinum as a current collector.
しかしながら、上記公報で用いている金や白金などの不
活性金属は非常に高価であるので電池コスト高を招くこ
とから実用には適さず、工業上利用への適用は困難とな
るばかりでなく、これら金属を蒸着するなどして電極面
に付着させる方法では集電部と電極との間に不純物が入
り込むため、この不純物の存在により自己放電が進んで
しまうという不都合もある。However, the inert metals used in the above publication, such as gold and platinum, are very expensive and lead to high battery costs, making them unsuitable for practical use. The method of attaching these metals to the electrode surface by vapor deposition or the like introduces impurities between the current collector and the electrode, which has the disadvantage that self-discharge progresses due to the presence of these impurities.
そこで、本発明のように電極の電池集電面と対向する面
を炭化させ、電極と炭素層とを直接接触する構成とすれ
ば、高い導電性をもち且つ不活・１（１で安価な炭素の
存在によって上記の如き酸化反応が抑制され、電池］ス
ト高を招くことなく自己放電の防止を効果的に図ること
ができる。しかも、本発明では導電性ポリマーの表面部
を炭化するのみで電極表面に炭素層が形成されるので、
特開昭５９−１１２５８４ 月のような手間のかかる蒸
着作業工程は不用となり、また集電体と電極との間に不
純物が入り込むことがないため、その分］ス１〜低減化
、並びに自己放電改善に効果がでる。Therefore, as in the present invention, if the surface of the electrode facing the battery current collecting surface is carbonized and the electrode and the carbon layer are in direct contact with each other, it is possible to achieve a structure that has high conductivity and is inert and inexpensive. The presence of carbon suppresses the above-mentioned oxidation reaction, making it possible to effectively prevent self-discharge without causing high battery stress.Furthermore, in the present invention, only the surface portion of the conductive polymer is carbonized. Since a carbon layer is formed on the electrode surface,
JP-A-59-112584 The time-consuming process of vapor deposition is no longer necessary, and impurities do not enter between the current collector and the electrode, resulting in a reduction in 1~ and self-discharge. Effective for improvement.
〈実施例〉
デーグラ−・プツタ触媒を用いてアセチレンからポリア
セチレンを合成し、得られた粒状物を円板状に成形した
。この成形物を真空中で表面温度６００ ’Ｃの熱根上
に数秒間接触させて片面を炭化させてその面に炭素層を
形成した。尚、このような炭化処理はアルゴンなどの不
活性ガス雰囲気中で行なってもよい。また、炭化処理に
使用した熱板は熱電対などのセンサーによりその表面温
度が均−且つ一定に制御されるものがよい。<Example> Polyacetylene was synthesized from acetylene using a Daegler-Putta catalyst, and the resulting granules were molded into a disk shape. This molded product was brought into contact with a hot root having a surface temperature of 600'C in vacuum for several seconds to carbonize one side and form a carbon layer on that surface. Note that such carbonization treatment may be performed in an inert gas atmosphere such as argon. Further, the hot plate used for the carbonization treatment is preferably one whose surface temperature is controlled to be uniform and constant by a sensor such as a thermocouple.
そして、第１図に示ずように、このように炭化処理した
円板状成形物を正極１として、またセパレータ２として
ガラスフィルタを用い、これらに公知のリチウム金属か
らなる負極３、絶縁バッキング４、正極缶５、正極集電
体６、負゛極缶７、負極集電体８等を組合せ、また電解
液としてホウフッ化リチウムをプロピレンカーボネイト
に溶解させたものを用い、正極１の炭化面を正極集電体
６側にして本発明に係る電池Ａを作製した二
また、正極１として炭化処理をしないほかは同様なポリ
アセチレン円板状成形物を使用し、他は同様な工程によ
って従来の電池Ｂを作製した。更に、正極１として同様
に炭化処理をしないポリアセチレン円板状成形物で、こ
の円板状成形物の正極集電体側面に金を５００人の厚さ
で蒸着したものを使用して同様な工程で比較用の電池Ｃ
を作製した。As shown in FIG. 1, the carbonized disk-shaped molded product was used as a positive electrode 1, a glass filter was used as a separator 2, and these were combined with a negative electrode 3 made of known lithium metal and an insulating backing 4. , the positive electrode can 5, the positive electrode current collector 6, the negative electrode can 7, the negative electrode current collector 8, etc., and using an electrolyte in which lithium fluoroborate was dissolved in propylene carbonate, the carbonized surface of the positive electrode 1 was heated. A battery A according to the present invention was prepared with the positive electrode current collector 6 side placed on the positive electrode 1. A similar polyacetylene disk-shaped molded product was used as the positive electrode 1, except that it was not carbonized, and a conventional battery was manufactured using the same process. B was produced. Furthermore, as the positive electrode 1, a polyacetylene disc-shaped molded product that was not subjected to carbonization treatment was used, and gold was vapor-deposited to a thickness of 500 mm on the side surface of the positive electrode current collector of this disc-shaped molded product, and the same process was carried out. Battery C for comparison
was created.
以上の３つの電池へ〜Ｃを夫々、電流１ｍＡで１時間充
電し、また電流１ｍＡで電池電圧２．ＯＶまで放電する
という１Ｊイクルを繰返した時の放電効率（％）のサイ
クルによる変化を調べ勾。Each of the above three batteries ~C was charged with a current of 1 mA for 1 hour, and the battery voltage was 2.5 mA with a current of 1 mA. We investigated the change in discharge efficiency (%) due to cycles when 1J cycles of discharging to OV were repeated.
この時のサイクル特性を第２図に示す。同図より、この
ように充放電容量が少ない場合に、は従来の電池Ｂでも
ある程度の＋ｊイクル寿命を持っているが、比較用の電
池Ｃでは電池Ｂの約１．５倍、本発明の電池Ａではその
２倍以上ものサイクル寿命をもっていることがわかる。The cycle characteristics at this time are shown in FIG. From the figure, when the charge/discharge capacity is small, even conventional battery B has a certain +j cycle life, but comparative battery C has a lifespan of about 1.5 times that of battery B, and that of the present invention. It can be seen that battery A has a cycle life that is more than twice that.
また、これら３つの電池Ａ−Ｃを夫々、電流１ｍＡで３
時間充電し、また電流１ｍＡで電池電圧？、０■まで放
電するという４Ｊイクルを繰返した時の充電効率（％）
のサイクルによる変化を調べた。この時のサイクル特性
は第３図に示した通りであり、このように充放電容量が
大きくなった場合には従来の電池Ｂでは３０ザイクル程
度のサイクル寿命しかないのに対し、比較用の電池Ｃで
は電池Ｂの２倍程度、また本発明の電池Ａでは電池Ｃと
較べても遥かに長いサイクル寿命を有し、サイクル寿命
の大幅な改善がなされたことがわかる。In addition, these three batteries A to C are each connected at a current of 1 mA for 3
After charging for an hour, what is the battery voltage at a current of 1mA? , charging efficiency (%) when 4J cycles of discharging to 0■ are repeated
The changes due to the cycle were investigated. The cycle characteristics at this time are as shown in Figure 3, and when the charge/discharge capacity is increased in this way, conventional battery B has a cycle life of only about 30 cycles, whereas the comparative battery has a cycle life of only about 30 cycles. It can be seen that battery C has a cycle life that is about twice that of battery B, and battery A of the present invention has a much longer cycle life than battery C, indicating that the cycle life has been significantly improved.
このような、電池Ａ、Ｃが電池Ｂに較べて良好なサイク
ル特性をもつのは前記したように一正極１と正極集電体
６あるいは負極３と負極缶７内面との間の接触抵抗が小
さいことによる。また電池へが電池Ｃに較べてサイクル
寿命が改善されているのは次の理由によるものと考えら
れる。すなわち、電池Ｃのように蒸着等によって集電層
を正極に接触させた場合、接触部を微視的にみると正極
表面の分子の一部に集電層に接触していないものが存在
し、このため正極−集電層間の集電効率が低いのに対し
、本発明の場合には正極１と炭素層との境界部にある導
電性ポリマー分子はほぼ完全に炭素層と接触しているた
めにその間の集電効率は非常に高くなる訳である。また
、蒸着等の方法を用いた場合には正極１と集電面との間
に不純物が混入し、このこともザイクル寿命低下の一因
となるのに対し、本発明の場合には不純物の入ることが
ほぼ皆無であるのでこの点もサイクル寿命向上に寄与し
ている。As mentioned above, the reason why batteries A and C have better cycle characteristics than battery B is that the contact resistance between the positive electrode 1 and the positive electrode current collector 6 or between the negative electrode 3 and the inner surface of the negative electrode can 7 is By being small. Furthermore, the reason why the cycle life of the battery is improved compared to the battery C is considered to be due to the following reason. In other words, when the current collecting layer is brought into contact with the positive electrode by vapor deposition or the like as in Battery C, if we look microscopically at the contact area, there are some molecules on the surface of the positive electrode that are not in contact with the current collecting layer. Therefore, the current collection efficiency between the positive electrode and the current collecting layer is low, whereas in the case of the present invention, the conductive polymer molecules at the boundary between the positive electrode 1 and the carbon layer are almost completely in contact with the carbon layer. Therefore, the current collection efficiency during that period becomes extremely high. In addition, when a method such as vapor deposition is used, impurities are mixed between the positive electrode 1 and the current collecting surface, which also causes a reduction in cycle life, whereas in the case of the present invention, impurities This also contributes to improving the cycle life, as there is almost no chance of any intrusion occurring.
また、第４図は電池Ａ〜Ｃを夫々充電後に室温で放置し
ておいた場合における電池容量（％）の経口４変化を示
したもので、従来の電池Ｂに較べて比較用の電池Ｃ及び
本発明の電池への自己放電率はかなり低く、また電池Ｃ
に較べて本発明の電池Ａの自己放電率が一段と低いこと
がわかる。このように電池Ａの自己放電率が電池Ｃに較
べてもかなり低く抑えられるのは、前述した如く、電極
と集電面との間に不純物が入ることが殆んどないことに
因るものと思われる。In addition, Figure 4 shows the changes in battery capacity (%) when batteries A to C are left at room temperature after being charged. Comparing battery C with conventional battery B, and the self-discharge rate to the battery of the present invention is quite low, and the battery C
It can be seen that the self-discharge rate of the battery A of the present invention is much lower than that of the battery A of the present invention. The reason why the self-discharge rate of Battery A is kept much lower than that of Battery C is that, as mentioned above, there are almost no impurities between the electrode and the current collecting surface. I think that the.
尚、この発明を負極に応用しても同様な効果が得られる
ことは明らかである。It is clear that similar effects can be obtained even when this invention is applied to a negative electrode.
〈発明の効果〉
以上のように構成されるこの発明の二次電池によれば、
電極の電池集電面と対向する面を炭化させた構成とした
ので、電池集電面と電極表面との集電面における接触性
が格段に向上することは勿論、充電中に充電電流が急上
臂する等といったことがないので、充放電容量増大、即
ち高エネルギー密度化、並びに電池サイクル寿命向上、
自己放電防止等を効果的に達成することができ、その工
業的価値は人である。<Effects of the Invention> According to the secondary battery of the present invention configured as described above,
Since the surface of the electrode facing the battery current collecting surface is carbonized, the contact between the battery current collecting surface and the electrode surface on the current collecting surface is greatly improved, and the charging current does not suddenly increase during charging. Since there is no need to bend over, the charge/discharge capacity is increased, which means higher energy density, and battery cycle life is improved.
Self-discharge prevention etc. can be effectively achieved, and its industrial value is human.
第１図はこの発明に係る電池の断面図、第２．３図は各
種電池のサイクル特性を示したグラフ、第４図は各種電
池の自己放電特性を説明するためのグラフである。
１・・・正極、３・・・負極、５・・・正極缶、７・・
・負極用。FIG. 1 is a cross-sectional view of a battery according to the present invention, FIGS. 2 and 3 are graphs showing the cycle characteristics of various batteries, and FIG. 4 is a graph for explaining the self-discharge characteristics of various batteries. 1... Positive electrode, 3... Negative electrode, 5... Positive electrode can, 7...
・For negative electrode.
Claims (1)
電池であつて、前記電極の電池集電面と対向する面を炭
化させてなることを特徴とする二次電池。1. A secondary battery having at least one electrode made of a conductive polymer, characterized in that the surface of the electrode facing the battery current collecting surface is carbonized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60178285A JPH065616B2 (en) | 1985-08-13 | 1985-08-13 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60178285A JPH065616B2 (en) | 1985-08-13 | 1985-08-13 | Secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6237873A true JPS6237873A (en) | 1987-02-18 |
| JPH065616B2 JPH065616B2 (en) | 1994-01-19 |
Family
ID=16045793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60178285A Expired - Lifetime JPH065616B2 (en) | 1985-08-13 | 1985-08-13 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH065616B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09106806A (en) * | 1996-10-18 | 1997-04-22 | Denso Corp | Battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59112584A (en) * | 1982-12-20 | 1984-06-29 | Showa Denko Kk | battery |
-
1985
- 1985-08-13 JP JP60178285A patent/JPH065616B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59112584A (en) * | 1982-12-20 | 1984-06-29 | Showa Denko Kk | battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09106806A (en) * | 1996-10-18 | 1997-04-22 | Denso Corp | Battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH065616B2 (en) | 1994-01-19 |
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| EXPY | Cancellation because of completion of term |