JPH115864A - Conductive polymer and its production - Google Patents
Conductive polymer and its productionInfo
- Publication number
- JPH115864A JPH115864A JP9159782A JP15978297A JPH115864A JP H115864 A JPH115864 A JP H115864A JP 9159782 A JP9159782 A JP 9159782A JP 15978297 A JP15978297 A JP 15978297A JP H115864 A JPH115864 A JP H115864A
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- solvent
- polymer
- polyaniline
- lithium perchlorate
- 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.)
- Withdrawn
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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Moulding By Coating Moulds (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】導電性高分子は、近年、二次
電池の正極材料、電磁波シールド材、センサー用半導体
素子、光記録材料等に広く利用されているが、本発明
は、化学的安定性に優れ、工業的応用価値の高いリチウ
ム二次電池用正極に用いられる導電性高分子とその製造
方法に関するものである。BACKGROUND OF THE INVENTION In recent years, conductive polymers have been widely used as cathode materials for secondary batteries, electromagnetic wave shielding materials, semiconductor devices for sensors, optical recording materials, and the like. The present invention relates to a conductive polymer used for a positive electrode for a lithium secondary battery having excellent industrial properties and a high industrial application value, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来より、原料であるアニリン等のモノ
マーを電気化学的に酸化重合する電解重合法、または原
料であるアニリン等のモノマーを酸化剤存在下で重合す
る化学酸化重合法で導電性高分子を合成することが一般
的に知られている。2. Description of the Related Art Conventionally, electroconductive polymerization is carried out by electrochemically oxidizing and polymerizing a monomer such as aniline as a raw material, or by chemical oxidative polymerization wherein a monomer such as aniline is polymerized in the presence of an oxidant. It is generally known to synthesize polymers.
【０００３】しかしながら、電解重合法では導電性高分
子の大量合成時に電解効率がかなり低下したり、大規模
な電解槽が必要とされる等の問題点があり、このため、
量産を必要とする製品では、化学酸化重合法による導電
性高分子の合成が必要である。ポリアニリン系物質の化
学酸化重合に関しては例えば特開平７−１７９５７８号
公報に開示されている。化学酸化重合法で得られたポリ
アニリンを用いて二次電池の正極材料を製造する場合、
ポリアニリン粉末を導電剤及びバインダと混合し、加圧
成形する方法や、ポリアニリン粉末の全量または一部を
有機溶媒に溶解して集電材に塗布する方法が一般的に採
用されている。[0003] However, the electropolymerization method has problems such as a considerable decrease in electrolysis efficiency when a large amount of conductive polymer is synthesized and a need for a large-scale electrolytic cell.
For products requiring mass production, it is necessary to synthesize a conductive polymer by a chemical oxidation polymerization method. The chemical oxidative polymerization of a polyaniline-based substance is disclosed in, for example, JP-A-7-179578. When producing a cathode material for a secondary battery using polyaniline obtained by a chemical oxidation polymerization method,
A method in which polyaniline powder is mixed with a conductive agent and a binder and pressure-molded, or a method in which the whole or a part of the polyaniline powder is dissolved in an organic solvent and applied to a current collector, are generally adopted.
【０００４】化学酸化重合法で得られた導電性高分子
は、その分子鎖がランダムに絡まった状態となってお
り、集電材上に高分子で、緻密な物理構造の正極が形成
されることになる。特に、加圧成形する場合には、その
緻密性が増大する。二次電池正極材料のように溶媒中の
イオンが導電性高分子鎖内を出入りすることで電池反応
が進行する場合、この緻密な構造は、正極内のイオン拡
散抵抗を増大させる要因となり、電池の性能が、サイク
ル充放電を頻繁に繰り返さないと向上し難いという問題
点があった。[0004] The conductive polymer obtained by the chemical oxidation polymerization method has a molecular chain in which the molecular chains are randomly entangled, and a polymer and a positive electrode having a dense physical structure are formed on the current collector. become. In particular, in the case of pressure molding, its denseness increases. When a battery reaction proceeds as ions in a solvent move in and out of the conductive polymer chain as in a secondary battery cathode material, this dense structure causes an increase in ion diffusion resistance in the cathode, and the battery However, there is a problem that the performance is difficult to improve unless the cycle charge / discharge is frequently repeated.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上述の緻密
な導電性高分子に細孔を形成することによって、二次電
池正極材料として用いた場合、従来の化学酸化重合法で
得られた導電性高分子に比較して正極内のイオン拡散抵
抗が低く、電池性能を飛躍的に向上できるような導電性
高分子及びその製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention, when used as a secondary battery positive electrode material by forming pores in the above-described dense conductive polymer, has been obtained by a conventional chemical oxidation polymerization method. It is an object of the present invention to provide a conductive polymer having a lower ion diffusion resistance in a positive electrode than a conductive polymer and capable of dramatically improving battery performance, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明は、この目的を達
成するために、 １） 化学酸化重合して得られる導電性高分子材の加圧
成形体中に分子サイズの微細な細孔を均一に分散して設
けてなる導電性高分子を提供し、 ２） 化学酸化重合して得られる導電性高分子を当該高
分子に対して１重量％乃至３０重量％の低分子化合物を
溶解させた溶剤に混合し、溶剤のみを蒸発させて低分子
化合物を均一に分散させた混合物を得た後、溶剤を使用
せずに加圧成形する（以下第１の方法という）、 ３） 化学酸化重合して得られる導電性高分子を当該高
分子に対して１重量％乃至３０重量％の低分子化合物及
び当該高分子に対して５重量％乃至３０重量％のバイン
ダーを溶解させた溶液に混合し、キャスト成形した後、
溶剤のみを蒸発させて成形する（以下第２の方法とい
う）、各方法を提供するものである。In order to achieve this object, the present invention provides: 1) fine pores of a molecular size in a pressure-formed body of a conductive polymer material obtained by chemical oxidation polymerization; (2) providing a conductive polymer obtained by uniformly dispersing a conductive polymer obtained by chemical oxidative polymerization, by dissolving 1 to 30% by weight of a low-molecular compound with respect to the polymer; Mixed with a mixed solvent, evaporating only the solvent to obtain a mixture in which the low molecular weight compound is uniformly dispersed, and then performing pressure molding without using a solvent (hereinafter referred to as a first method), 3) chemical oxidation A conductive polymer obtained by polymerization is mixed with a solution in which a low-molecular compound of 1% to 30% by weight and a binder of 5% to 30% by weight of the polymer are dissolved. After casting,
The present invention provides each method of forming by evaporating only the solvent (hereinafter referred to as a second method).
【０００７】本発明の導電性高分子によれば、化学酸化
重合して得られた従来の緻密な導電性高分子に対して分
子サイズで形成されるような微細な細孔が形成されてい
るので、正極内のイオン拡散抵抗が低くなり、電池性能
を飛躍的に向上させることが可能な導電性高分子が提供
できる。本発明に係る第１の方法では粉末を加圧成形す
るだけで容易に電極を成形することが可能である。更に
第２の方法ではキャスト成形機や大型の乾燥機を必要と
するが、大面積化や連続生産が可能となる。[0007] According to the conductive polymer of the present invention, fine pores having a molecular size formed with respect to a conventional dense conductive polymer obtained by chemical oxidation polymerization are formed. Therefore, it is possible to provide a conductive polymer that has a low ion diffusion resistance in the positive electrode and can dramatically improve battery performance. In the first method according to the present invention, it is possible to easily form the electrode only by pressing the powder under pressure. Furthermore, the second method requires a cast molding machine and a large-sized dryer, but allows for a large area and continuous production.
【０００８】[0008]
【発明の実施の形態】本発明に係る方法で用いられる導
電性高分子としては、ポリアニリン、ポリチオフェン、
ポリピロールなどが挙げられる。その重合度は、ポリア
ニリン１００〜５，０００、ポリチオフェン１００〜
５，０００、ポリピロール１００〜５，０００である。
このうち、ポリアニリンの原料モノマーとしては無置換
または芳香族にアルキル基が置換されたアニリンなどが
挙げられるが、さらにこれらのアニリンは、特開平７−
１７９５７８号公報に記載されているように、リチウム
イオンと反応するドーパント物質としてアルキルスルホ
ン酸が複合化されていてもよい。その組成比は例えばポ
リアニリン：アルキルスルホン酸＝２：１ｍｏｌ％であ
る。また、低分子化合物としては、リチウム塩、好まし
くは二次電池の電解液の性能を阻害しない電解質、例え
ば過塩素酸リチウム、四フッ化ホウ素酸リチウム、六フ
ッ化リン酸リチウムなどが挙げられる。低分子化合物
は、十分な効果が得られるために導電性高分子に対して
外割りで１％以上とし、正極の成形性を維持し、剥離等
を防止するために３０％以下とするのが望ましい。ま
た、低分子を溶解する溶剤としては、第１の方法では低
分子化合物のみを溶解し、蒸発させ易い溶剤であればよ
く、具体的には、アセトン、アセトニトリル、ニトロメ
タンがあり、中でもアセトンが好ましい。第２の方法で
は低分子化合物とバインダーの両方を溶解させる必要が
あり、具体的には、Ｎ−メチルピロリドン（ＮＭＰ）、
Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）、Ｎ，Ｎ−
ジメチルホルムアミド（ＤＭＦ）があり、中でもＮＭＰ
が好ましい。第２の方法で用いるバインダーとしては例
えばポリフッ化ビニリデン（ＰＶＤＦ）又はそれらと同
効のものが好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The conductive polymer used in the method according to the present invention includes polyaniline, polythiophene,
And polypyrrole. The polymerization degree is polyaniline 100-5,000, polythiophene 100-
5,000, polypyrrole 100-5,000.
Among them, as a raw material monomer for polyaniline, aniline and the like which are unsubstituted or aromatically substituted with an alkyl group may be mentioned.
As described in 179578, an alkyl sulfonic acid may be compounded as a dopant substance that reacts with lithium ions. The composition ratio is, for example, polyaniline: alkylsulfonic acid = 2: 1 mol%. Examples of the low molecular compound include a lithium salt, preferably an electrolyte that does not hinder the performance of the electrolytic solution of the secondary battery, such as lithium perchlorate, lithium tetrafluoroborate, and lithium hexafluorophosphate. The low molecular weight compound should be 1% or more in terms of the conductive polymer in order to obtain a sufficient effect, and 30% or less in order to maintain the moldability of the positive electrode and prevent peeling. desirable. In addition, as the solvent for dissolving the low-molecular compound, any solvent that dissolves only the low-molecular compound in the first method and is easy to evaporate may be used. Specific examples include acetone, acetonitrile, and nitromethane. . In the second method, both the low-molecular compound and the binder need to be dissolved, and specifically, N-methylpyrrolidone (NMP),
N, N-dimethylacetamide (DMAC), N, N-
There is dimethylformamide (DMF), especially NMP
Is preferred. As the binder used in the second method, for example, polyvinylidene fluoride (PVDF) or a binder having the same effect as those is preferable.
【０００９】本発明に係る導電性高分子の製造方法で
は、第１及び第２のいずれの方法においても、まず、化
学酸化重合して得られた導電性高分子に、溶剤に溶解さ
せた例えば過塩素酸リチウムのような低分子化合物を均
一に分散混合させ、混合溶液を導電性高分子の粒子間及
び分子鎖間に浸透させ、分子サイズで均一に分散させ
る。次いで、本発明に係る第１の方法では、混合溶液ま
たはスラリーを乾燥させ、粉末状にした後、集電材上に
加圧成形する。加圧成形は、金属製の型に集電材を設置
し、上記混合粉末を所定量加えた後、プレス機を用いて
約５００〜２，０００ｋｇｆ／ｃｍ2 の圧力で行う。こ
の加圧成形物（電極）を電解液に浸漬すると、元の三次
元構造を維持したままで導電性高分子の粒子間及び高分
子鎖間から低分子化合物のみが溶出する。したがって、
加圧成形された導電性高分子には、低分子化合物が占有
していた跡に対応する微細な細孔が形成される。この大
きさは、低分子化合物の高分子への浸透状態や乾燥時の
析出粒径及び分散状態で変化するが、数μｍ以下であ
る。In the method for producing a conductive polymer according to the present invention, in any of the first and second methods, first, for example, a conductive polymer obtained by chemical oxidative polymerization is dissolved in a solvent. A low molecular compound such as lithium perchlorate is uniformly dispersed and mixed, and the mixed solution is permeated between the conductive polymer particles and between the molecular chains to be uniformly dispersed in the molecular size. Next, in the first method according to the present invention, the mixed solution or slurry is dried to be powdered, and then pressure-formed on a current collector. Pressure molding is performed by placing a current collector in a metal mold, adding a predetermined amount of the mixed powder, and then using a press at a pressure of about 500 to 2,000 kgf / cm 2 . When this pressed product (electrode) is immersed in the electrolytic solution, only the low-molecular compound is eluted from between the conductive polymer particles and between the polymer chains while maintaining the original three-dimensional structure. Therefore,
Fine pores corresponding to the trace occupied by the low-molecular compound are formed in the conductive polymer formed by pressure molding. This size varies depending on the state of penetration of the low-molecular compound into the polymer, the precipitated particle size at the time of drying, and the dispersion state, but is several μm or less.
【００１０】本発明に係る第２の方法においても同様
に、溶剤に溶解させた例えば過塩素酸リチウムのような
低分子化合物とバインダーを、化学酸化重合して得られ
た導電性高分子に、均一に分散混合させ、導電性高分子
の粒子間及び分子鎖間に浸透させ、分子サイズで均一に
分散させる。こうして得られた混合溶液またはスラリー
を集電材上にキャストした後、溶剤を蒸発させると、固
体状で導電性化合物及び低分子化合物が均一に複合化さ
れた緻密な三次元構造の正極材料が得られる。これを電
解液に浸漬すると、元の三次元構造を維持したままで導
電性高分子の粒子間及び高分子鎖間から低分子化合物の
みが溶出する。したがって、加圧成形された導電性高分
子には、低分子化合物が占有していた跡に対応する微細
な細孔が形成される。この大きさは、低分子化合物の高
分子への浸透状態や乾燥時の析出粒径及び分散状態で変
化するが、数μｍ以下である。Similarly, in the second method according to the present invention, a conductive polymer obtained by chemically oxidatively polymerizing a low molecular compound such as lithium perchlorate and a binder dissolved in a solvent is added to the conductive polymer. Uniformly disperse and mix, penetrate between conductive polymer particles and between molecular chains, and uniformly disperse in molecular size. The resulting mixed solution or slurry is cast on a current collector, and then the solvent is evaporated to obtain a solid cathode material having a dense three-dimensional structure in which the conductive compound and the low-molecular compound are uniformly compounded. Can be When this is immersed in the electrolytic solution, only the low-molecular compound is eluted from between the conductive polymer particles and between the polymer chains while maintaining the original three-dimensional structure. Therefore, fine pores corresponding to the trace occupied by the low-molecular compound are formed in the conductive polymer molded by pressure. This size varies depending on the state of penetration of the low-molecular compound into the polymer, the precipitated particle size at the time of drying, and the dispersion state, but is several μm or less.
【００１１】以上のように、本発明に係る導電性高分子
の製造方法では、第１及び第２のいずれの方法において
も、導電性高分子に適当な大きさの空隙が形成され、電
解液中のイオン、例えばリチウムイオンや過塩素酸イオ
ンなどの拡散抵抗が減少する。このため、導電性高分子
中のイオンが容易に移動できるようになり、イオンと導
電性高分子活性部位との反応がスムーズに行われるよう
になる。これにより、電池内部抵抗に影響を及ぼす反応
拡散抵抗が減少し、充放電反応が理想的に行われる。As described above, in the method for producing a conductive polymer according to the present invention, in any of the first and second methods, a gap of an appropriate size is formed in the conductive polymer, and The diffusion resistance of the ions therein, such as lithium ions and perchlorate ions, decreases. For this reason, the ions in the conductive polymer can easily move, and the reaction between the ions and the conductive polymer active site can be smoothly performed. Thereby, the reaction diffusion resistance which affects the internal resistance of the battery is reduced, and the charge / discharge reaction is ideally performed.
【００１２】[0012]
【実施例】以下に本発明に係る導電性高分子の製造方法
の実施例を示すが、本発明はこれらの実施例により限定
されるものではない。 実施例１ ポリアニリンの原料モノマーであるアニリン５．５９ｇ
（６０ｍｍｏｌ）を６０ｗｔ％の過塩素酸１３．４ｇ
（８０ｍｍｏｌ）を溶解したイオン交換水６０ｍｌに加
え、０℃に冷却しながら窒素置換した。次に酸化剤とし
て１．６ｍｏｌ／リットルの過硫酸アンモニウム水溶液
６４．０ｇを約１時間で滴下した後、５時間攪拌混合し
た。このポリアニリンをイオン交換水２００ｍｌに約２
時間浸漬し、４Ｇのガラスフィルターで固形分３．５ｇ
を得た後、固形分を真空乾燥器で脱水し、ポリアニリン
粉末を得た。EXAMPLES Examples of the method for producing a conductive polymer according to the present invention will be described below, but the present invention is not limited to these examples. Example 1 5.59 g of aniline which is a raw material monomer of polyaniline
(60 mmol) to 13.4 g of 60 wt% perchloric acid
(80 mmol) was dissolved in 60 ml of ion-exchanged water, and the mixture was cooled to 0 ° C. and replaced with nitrogen. Next, 64.0 g of a 1.6 mol / liter ammonium persulfate aqueous solution as an oxidizing agent was added dropwise in about 1 hour, and the mixture was stirred and mixed for 5 hours. About 200 ml of this polyaniline is added to 200 ml of deionized water.
Immersion for 3.5 hours, 3.5g solid content with 4G glass filter
After the solid was obtained, the solid content was dehydrated with a vacuum drier to obtain a polyaniline powder.
【００１３】このポリアニリン粉末３．０ｇを、過塩素
酸リチウム０．３ｇを溶解させたアセトン約３０ｍｌ中
に混合浸漬した後、アセトンを室温で蒸発させて混合粉
末を得た。この粉末を炭素繊維で構成された集電材状に
分散させ、プレス機を用いて１，０００ｋｇｆ／ｃｍ2
の圧力で加圧成形した。次に、この材料を二次電池用の
電解液である過塩素酸リチウム１ｍｏｌ／ｌを溶解した
炭酸プロピレン溶液中に一昼夜浸漬し、ポリアニリン中
の過塩素酸リチウムを電解液中に溶出させて正極材料を
得た。このようにして得られた正極材料とＬｉ−Ａｌ合
金負極及びセパレータを組み合わせてセルを作製した。
このセルを交流インピーダンス法で測定して得られたｃ
ｏｌｅ−ｃｏｌｅプロットから、反応拡散抵抗に起因す
る円弧の虚数部と周波数の平方根の逆数との間に直線関
係があると仮定して、その勾配を求めることからみかけ
の拡散定数（Ｄ）を算出した。After mixing and immersing 3.0 g of the polyaniline powder in about 30 ml of acetone in which 0.3 g of lithium perchlorate was dissolved, acetone was evaporated at room temperature to obtain a mixed powder. This powder was dispersed into a current collector made of carbon fiber, and was then subjected to 1,000 kgf / cm 2 using a press machine.
Under pressure. Next, this material was immersed all day and night in a propylene carbonate solution in which 1 mol / l of lithium perchlorate as an electrolyte for a secondary battery was dissolved, and lithium perchlorate in polyaniline was eluted into the electrolyte to form a positive electrode. The material was obtained. A cell was fabricated by combining the positive electrode material thus obtained, the Li-Al alloy negative electrode, and the separator.
C obtained by measuring this cell by the AC impedance method
Assuming that there is a linear relationship between the imaginary part of the arc caused by the reaction diffusion resistance and the reciprocal of the square root of the frequency, an apparent diffusion constant (D) is calculated from the ole-cole plot by calculating the gradient thereof. did.
【００１４】比較のために過塩素酸リチウムを添加しな
い以外は実施例１と同様にして得られた正極材料を用い
てセルを作製し、交流インピーダンス法で測定して得ら
れたｃｏｌｅ−ｃｏｌｅプロットからみかけの拡散定数
（Ｄ）を算出した。以上の結果を表１に示す。表１によ
れば、過塩素酸リチウムを添加した場合は添加しない場
合に比較してみかけの拡散定数（Ｄ）が１５倍増加して
おり、明らかに反応拡散抵抗を低減する効果が実施例１
に示されている。For comparison, a cell was prepared using a positive electrode material obtained in the same manner as in Example 1 except that lithium perchlorate was not added, and a cole-cole plot obtained by measurement by an AC impedance method. The apparent diffusion constant (D) was calculated. Table 1 shows the above results. According to Table 1, when lithium perchlorate was added, the apparent diffusion constant (D) was increased by a factor of 15 as compared with the case where lithium perchlorate was not added.
Is shown in
【００１５】実施例２ ポリアニリンに代えてポリチオフェン、ポリピロール、
ポリアニリン／エタンジスルホン酸複合体をそれぞれ用
いた以外は実施例１と同様にして得られた正極材料を用
いてセルを作製し、交流インピーダンス法で測定した得
られたたｃｏｌｅ−ｃｏｌｅプロットからみかけの拡散
定数（Ｄ）を算出した。また、比較のために過塩素酸リ
チウムを添加しない以外は上記と同様にして得られた正
極材料を用いてセルを作製し、交流インピーダンス法で
測定して得られたｃｏｌｅ−ｃｏｌｅプロットからみか
けの拡散定数（Ｄ）を算出した。以上の結果を表１に併
記する。表１によれば、導電性高分子の種類を変えても
過塩素酸リチウムを添加した場合は添加しない場合に比
較してみかけの拡散定数（Ｄ）が増加しており、反応拡
散抵抗を低減する効果が実施例２に示されている。Example 2 Instead of polyaniline, polythiophene, polypyrrole,
A cell was prepared using the positive electrode material obtained in the same manner as in Example 1 except that the polyaniline / ethanedisulfonic acid composite was used, and an apparent cole-cole plot measured by an AC impedance method was used. The diffusion constant (D) was calculated. Also, for comparison, a cell was prepared using the positive electrode material obtained in the same manner as described above except that lithium perchlorate was not added, and an apparent cole-cole plot was obtained by measurement using an AC impedance method. The diffusion constant (D) was calculated. The results are shown in Table 1. According to Table 1, even when the kind of the conductive polymer was changed, the apparent diffusion constant (D) was increased when lithium perchlorate was added as compared with the case where lithium perchlorate was not added, and the reaction diffusion resistance was reduced. The effect of this is shown in the second embodiment.
【００１６】[0016]
【表１】 [Table 1]
【００１７】実施例３ ポリアニリンに代えて実施例２のポリアニリン／エタン
ジスルホン酸複合体を用い、表２に示す量の過塩素酸リ
チウム、四フッ化ホウ素酸リチウムおよび六フッ化リン
酸リチウムを用いて実施例１と同様にして得られた正極
材料を用いてセルを作製し、交流インピーダンス法で測
定して得られたｃｏｌｅ−ｃｏｌｅプロットからみかけ
の拡散定数（Ｄ）を算出した。また、比較のために過塩
素酸リチウムを添加しない以外は上記と同様にして得ら
れた正極材料を用いてセルを作製し、交流インピーダン
ス法で測定して得られたｃｏｌｅ−ｃｏｌｅプロットか
らみかけの拡散定数（Ｄ）を算出した。以上の結果を表
２に示す。表２によれば、導電性高分子に添加する低分
子化合物の種類を変えても低分子を添加した場合は添加
しない場合に比較してみかけの拡散定数（Ｄ）が増加し
ており、反応拡散抵抗を低減する効果が実施例３に示さ
れている。また、上記低分子化合物の添加量としては、
１〜３０重量％、特に３〜２０重量％が適当であること
が示されている。この添加量が１重量％未満では効果が
不充分であり、３０重量％を超えると、正極の成形性が
悪く、剥離等が起こり易くなり、５０重量％では正極の
成形が困難で測定ができなかった。Example 3 The polyaniline / ethanedisulfonic acid complex of Example 2 was used instead of polyaniline, and the amounts of lithium perchlorate, lithium tetrafluoroborate and lithium hexafluorophosphate shown in Table 2 were used. A cell was manufactured using the positive electrode material obtained in the same manner as in Example 1, and an apparent diffusion constant (D) was calculated from a cole-col plot obtained by measurement by an AC impedance method. Also, for comparison, a cell was prepared using the positive electrode material obtained in the same manner as described above except that lithium perchlorate was not added, and an apparent cole-cole plot was obtained by measurement using an AC impedance method. The diffusion constant (D) was calculated. Table 2 shows the above results. According to Table 2, even when the type of the low molecular compound added to the conductive polymer was changed, the apparent diffusion constant (D) increased when the low molecule was added as compared with the case where the low molecule was not added. The effect of reducing the diffusion resistance is shown in the third embodiment. In addition, the amount of the low molecular compound added,
1 to 30% by weight, especially 3 to 20% by weight, has been shown to be suitable. If the addition amount is less than 1% by weight, the effect is insufficient. If it exceeds 30% by weight, the moldability of the positive electrode is poor and peeling is likely to occur. Did not.
【００１８】[0018]
【表２】 [Table 2]
【００１９】実施例４ このポリアニリン粉末３．０ｇを、過塩素酸リチウム
０．３ｇとバインダー（ＰＶＤＦ）０．３ｇを溶解させ
たＮＭＰ溶液約１０ｍｌ中に混合浸漬した後、炭素繊維
で構成された集電材状にキャスト成形し、ＮＭＰを１０
０℃の乾燥器内で蒸発させてキャスト成形膜を得た。こ
のキャスト成形膜を正極として、実施例１と同様にセル
を作製し、交流インピーダンス法で測定した得られたｃ
ｏｌｅ−ｃｏｌｅプロットから見かけの拡散定数（Ｄ）
を算出した。。比較のために過塩素酸リチウムを添加し
ない以外は実施例４と同様にして得られた正極材料を用
いてセルを作製し、交流インピーダンス法で測定して得
られたｃｏｌｅ−ｃｏｌｅプロットからみかけの拡散定
数（Ｄ）を算出した。以上の結果を表３に示す。表３に
よれば、過塩素酸リチウムを添加した場合は添加しない
場合に比較してみかけの拡散定数（Ｄ）が２５倍増加し
ており、明らかに反応拡散抵抗を低減する効果が実施例
４に示されている。Example 4 3.0 g of this polyaniline powder was mixed and immersed in about 10 ml of an NMP solution in which 0.3 g of lithium perchlorate and 0.3 g of a binder (PVDF) were dissolved, and then the mixture was made of carbon fibers. Cast into current collector material, NMP 10
Evaporation was performed in a dryer at 0 ° C. to obtain a cast film. Using this cast molded film as a positive electrode, a cell was prepared in the same manner as in Example 1, and the obtained c was measured by an AC impedance method.
Diffusion constant apparent from ole-cole plot (D)
Was calculated. . For comparison, a cell was produced using the positive electrode material obtained in the same manner as in Example 4 except that lithium perchlorate was not added, and an apparent cole-cole plot was obtained by measurement using an AC impedance method. The diffusion constant (D) was calculated. Table 3 shows the above results. According to Table 3, the apparent diffusion constant (D) was increased by 25 times when lithium perchlorate was added as compared with the case where lithium perchlorate was not added. Is shown in
【００２０】実施例５ ポリアニリンに代えて実施例２の３種類の導電性高分子
をそれぞれ用いた以外は実施例４と同様にして得られた
正極材料を用いてセルを作製し、交流インピーダンス法
で測定して得られたたｃｏｌｅ−ｃｏｌｅプロットから
みかけの拡散定数（Ｄ）を算出した。また、比較のため
に過塩素酸リチウムを添加しない以外は上記と同様にし
て得られた正極材料を用いてセルを作製し、交流インピ
ーダンス法で測定したｃｏｌｅ−ｃｏｌｅプロットから
みかけの拡散定数（Ｄ）を算出した。以上の結果を表３
に併記する。表３によれば、導電性高分子の種類を変え
ても過塩素酸リチウムを添加した場合は添加しない場合
に比較してみかけの拡散定数（Ｄ）が増加していること
を示しており、反応拡散抵抗を低減する効果が実施例５
に示されている。Example 5 A cell was prepared using the positive electrode material obtained in the same manner as in Example 4 except that the three kinds of conductive polymers of Example 2 were used instead of polyaniline, and an AC impedance method was used. The apparent diffusion constant (D) was calculated from the cole-colle plot obtained by the measurement in (1). For comparison, a cell was prepared using the positive electrode material obtained in the same manner as described above except that lithium perchlorate was not added, and an apparent diffusion constant (D ) Was calculated. Table 3 shows the above results.
It is described together. According to Table 3, even when the type of the conductive polymer was changed, the apparent diffusion constant (D) was increased when lithium perchlorate was added as compared with the case where lithium perchlorate was not added, Example 5 shows the effect of reducing the reaction diffusion resistance.
Is shown in
【００２１】[0021]
【表３】 [Table 3]
【００２２】実施例６ ポリアニリンに代えて実施例２のポリアニリン／エタン
ジスルホン酸複合体を用い、表４に示す量の過塩素酸リ
チウム、四フッ化ホウ素酸リチウムおよび六フッ化リン
酸リチウムを用いて実施例４と同様にして得られた正極
材料を用いてセルを作製し、交流インピーダンス法で測
定して得られたたｃｏｌｅ−ｃｏｌｅプロットからみか
けの拡散定数（Ｄ）を算出した。また、比較のために過
塩素酸リチウムを添加しない以外は上記と同様にして得
られた正極材料を用いてセルを作製し、交流インピーダ
ンス法で測定して得られたｃｏｌｅ−ｃｏｌｅプロット
からみかけの拡散定数（Ｄ）を算出した。以上の結果を
表４に示す。表４によれば、導電性高分子の種類を変え
ても過塩素酸リチウムを添加した場合は添加しない場合
に比較してみかけの拡散定数（Ｄ）が増加しており、反
応拡散抵抗を低減する効果が実施例６に示されている。
また、上記低分子化合物の添加量としては、１〜３０重
量％、特に３〜２０重量％が適当であることが示されて
いる。この添加量が１重量％未満では効果が不充分であ
り、３０重量％を超えると、正極の成形性が悪く、剥離
等が起こり易くなり、５０重量％では正極の成形が困難
で測定ができなかった。Example 6 The polyaniline / ethanedisulfonic acid complex of Example 2 was used instead of polyaniline, and the amounts of lithium perchlorate, lithium tetrafluoroborate and lithium hexafluorophosphate shown in Table 4 were used. A cell was produced using the positive electrode material obtained in the same manner as in Example 4, and an apparent diffusion constant (D) was calculated from a cole-col plot obtained by measurement by an AC impedance method. Also, for comparison, a cell was prepared using the positive electrode material obtained in the same manner as described above except that lithium perchlorate was not added, and an apparent cole-cole plot was obtained by measurement using an AC impedance method. The diffusion constant (D) was calculated. Table 4 shows the above results. According to Table 4, even when the type of the conductive polymer was changed, the apparent diffusion constant (D) increased when lithium perchlorate was added as compared with the case where lithium perchlorate was not added, and the reaction diffusion resistance was reduced. The effect of this is shown in the sixth embodiment.
It is also shown that the amount of the low molecular compound to be added is suitably 1 to 30% by weight, particularly 3 to 20% by weight. If the addition amount is less than 1% by weight, the effect is insufficient. If it exceeds 30% by weight, the moldability of the positive electrode is poor and peeling is likely to occur. Did not.
【００２３】[0023]
【表４】 [Table 4]
【００２４】[0024]
【発明の効果】以上、詳述したように、本発明によって
緻密な導電性高分子に微細な細孔が形成することで、正
極内のイオン拡散抵抗を低減し、電池性能を飛躍的に向
上させることができた。As described above in detail, by forming fine pores in a dense conductive polymer according to the present invention, the ion diffusion resistance in the positive electrode is reduced, and the battery performance is dramatically improved. I was able to.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成９年８月２６日[Submission date] August 26, 1997
【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】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】[0018]
【表２】 [Table 2]
【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[Correction target item name] 0023
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２３】[0023]
【表４】 [Table 4]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田坂 佳之 神奈川県横浜市金沢区幸浦一丁目８番地１ 三菱重工業株式会社基盤技術研究所内 (72)発明者 上田 隆 神奈川県横浜市金沢区幸浦一丁目８番地１ 三菱重工業株式会社基盤技術研究所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Yoshiyuki Tasaka 1-8-1 Koura, Kanazawa-ku, Yokohama-shi, Kanagawa Prefecture Inside the Research Center for Basic Technology Mitsubishi Heavy Industries, Ltd. 8-1 Inside Mitsubishi Heavy Industries, Ltd. Basic Technology Research Laboratory
Claims (3)
材の加圧成形体中に分子サイズの微細な細孔を均一に分
散して設けてなる導電性高分子。1. A conductive polymer obtained by uniformly dispersing fine pores having a molecular size in a pressure-formed body of a conductive polymer material obtained by chemical oxidation polymerization.
を当該高分子に対して１重量％乃至３０重量％の低分子
化合物を溶解させた溶剤に混合し、溶剤のみを蒸発させ
て低分子化合物を均一に分散させた混合物を得た後、溶
剤を使用せずに加圧成形することを特徴とする導電性高
分子の製造方法。2. A method according to claim 1, wherein the conductive polymer obtained by the chemical oxidative polymerization is mixed with a solvent in which a low molecular compound of 1% to 30% by weight is dissolved with respect to the polymer, and only the solvent is evaporated. A method for producing a conductive polymer, comprising: obtaining a mixture in which a molecular compound is uniformly dispersed, followed by pressure molding without using a solvent.
を当該高分子に対して１重量％乃至３０重量％の低分子
化合物及び当該高分子に対して５重量％乃至３０重量％
のバインダーを溶解させた溶液に混合し、キャスト成形
した後、溶剤のみを蒸発させて成形することを特徴とす
る導電性高分子の製造方法。3. A conductive polymer obtained by chemical oxidative polymerization, comprising 1 to 30% by weight of the low molecular compound based on the polymer and 5 to 30% by weight based on the polymer.
A method for producing a conductive polymer, comprising: mixing a solution in which a binder is dissolved, casting the mixture, and evaporating only the solvent to form the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9159782A JPH115864A (en) | 1997-06-17 | 1997-06-17 | Conductive polymer and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9159782A JPH115864A (en) | 1997-06-17 | 1997-06-17 | Conductive polymer and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH115864A true JPH115864A (en) | 1999-01-12 |
Family
ID=15701160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9159782A Withdrawn JPH115864A (en) | 1997-06-17 | 1997-06-17 | Conductive polymer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH115864A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009040478A1 (en) * | 2007-09-28 | 2009-04-02 | Valtion Teknillinen Tutkimuskeskus | Novel material, process for manufacturing thereof and new uses |
-
1997
- 1997-06-17 JP JP9159782A patent/JPH115864A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009040478A1 (en) * | 2007-09-28 | 2009-04-02 | Valtion Teknillinen Tutkimuskeskus | Novel material, process for manufacturing thereof and new uses |
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