JPH11269390A - Electroconductive resin composition and its alkali treatment - Google Patents
Electroconductive resin composition and its alkali treatmentInfo
- Publication number
- JPH11269390A JPH11269390A JP10071626A JP7162698A JPH11269390A JP H11269390 A JPH11269390 A JP H11269390A JP 10071626 A JP10071626 A JP 10071626A JP 7162698 A JP7162698 A JP 7162698A JP H11269390 A JPH11269390 A JP H11269390A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- conductive resin
- sulfonic acid
- lithium
- alkali
- 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- Withdrawn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
- Compositions Of Macromolecular Compounds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はポリマーバッテリー
の電極活物質として有用な導電性樹脂組成物のアルカリ
処理方法及び該処理によって得られるアルカリ処理導電
性樹脂組成物に関する。The present invention relates to a method for treating a conductive resin composition which is useful as an electrode active material for a polymer battery with an alkali, and an alkali-treated conductive resin composition obtained by the treatment.
【０００２】[0002]
【従来の技術】１９６１年頃、有機高分子であるポリア
セチレンが高い導電性を示すことが明らかとなり、その
後、多数の導電性ポリマーが報告されている。これらの
導電性ポリマーが二次電池の活物質として使用できるこ
とが報告されて以来、高エネルギー密度の二次電池を開
発する試みがなされてきた。１９８７年には、ポリアニ
リンを用いた二次電池が市場に現れ、本発明者らもすで
に、導電性ポリマー中にスルホン酸基を１個又は２個含
有するアニオン性低分子量化合物であるアルキルスルホ
ン酸を分散含有した導電性樹脂組成物が二次電池の電極
活物質として優れていることを見出している（特開平６
−１６８６７号、特開平７−１７９５７８号各公報）。
しかしながら、近年の二次電池に対する高性能化や長寿
命化の要求が厳しくなってきたことから、電極活物質と
して使用する場合に、さらに高いサイクル寿命を有する
導電性樹脂組成物あるいは導電性樹脂組成物のサイクル
寿命を向上させる処理技術の要求が高まってきている。2. Description of the Related Art Around 1961, it was found that polyacetylene, which is an organic polymer, exhibited high conductivity. Thereafter, a large number of conductive polymers have been reported. Since it was reported that these conductive polymers can be used as an active material of a secondary battery, attempts have been made to develop a secondary battery with a high energy density. In 1987, a secondary battery using polyaniline appeared on the market, and the present inventors have already found that an alkylsulfonic acid, which is an anionic low molecular weight compound containing one or two sulfonic acid groups in a conductive polymer. Has been found to be excellent as an electrode active material for a secondary battery.
-16867, JP-A-7-179578).
However, in recent years, demands for higher performance and longer life for secondary batteries have become more stringent, and therefore, when used as an electrode active material, a conductive resin composition or a conductive resin composition having a higher cycle life. There is an increasing demand for processing techniques to improve the cycle life of objects.
【０００３】[0003]
【発明が解決しようとする課題】本発明はこのような従
来技術の実状に鑑み、導電性ポリマー中にアルキルスル
ホン酸を分散含有した導電性樹脂組成物を電極活物質と
して使用する際に、サイクル寿命を向上させることがで
きる処理方法及びそれによってサイクル寿命が向上した
導電性樹脂組成物を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned situation of the prior art, and has been found to be effective in using a conductive resin composition containing an alkylsulfonic acid dispersed in a conductive polymer as an electrode active material. It is an object of the present invention to provide a treatment method capable of improving the life and a conductive resin composition having an improved cycle life.
【０００４】[0004]
【課題を解決するための手段】前記の導電性ポリマー中
にアルキルスルホン酸を分散含有した導電性樹脂組成
物、例えばポリアニリンにエタンジスルホン酸を分散含
有させた導電性樹脂組成物を二次電池の電極活物質とし
て使用するためには電極の形状に成形する必要がある。
ところがこれらの導電性樹脂組成物は溶媒に不溶なた
め、そのままでは成形することができないという問題が
あった。本発明者らは、これらの導電性樹脂組成物の成
形方法について種々検討の結果、アンモニア水−アセト
ン溶液で処理することにより、前記導電性樹脂組成物が
部分的に溶媒に可溶となり、電極の成形が可能になるこ
とを見出している。この方法により成形した電極は、優
れた性能を有しているが、サイクル劣化率がやや高く、
一層のサイクル寿命の改善が望まれた。そこで、本発明
者らはさらに検討を進め、リチウム系化合物を用いてア
ルカリ処理することによって、成形も容易で、しかもサ
イクル寿命が向上することを見出し、本発明を完成する
に至った。SUMMARY OF THE INVENTION A conductive resin composition containing an alkylsulfonic acid dispersed in the above-mentioned conductive polymer, for example, a conductive resin composition containing ethanedisulfonic acid dispersed in polyaniline, is used for a secondary battery. In order to use it as an electrode active material, it is necessary to shape it into an electrode shape.
However, there is a problem that these conductive resin compositions cannot be molded as they are because they are insoluble in a solvent. The present inventors have conducted various studies on molding methods of these conductive resin compositions, and as a result of treating them with an aqueous ammonia-acetone solution, the conductive resin composition became partially soluble in a solvent, and an electrode was formed. Has been found to be possible. The electrode formed by this method has excellent performance, but the cycle deterioration rate is slightly higher,
Further improvement in cycle life was desired. Thus, the present inventors have further studied and found that by performing alkali treatment using a lithium-based compound, molding is easy and cycle life is improved, and the present invention has been completed.
【０００５】すなわち、本発明の第１は、導電性ポリマ
ー中に、スルホン酸基を１個又は２個有するアルキルス
ルホン酸を、前記導電性ポリマーを構成するモノマー１
分子当たりのスルホン酸基の数が０．０６〜０．６とな
るような割合で分散含有した導電性樹脂組成物を、水酸
化リチウム又はリチウムアルコキシドの溶液で処理する
ことを特徴とする導電性樹脂組成物のアルカリ処理方法
である。That is, a first aspect of the present invention is that an alkyl sulfonic acid having one or two sulfonic acid groups is contained in a conductive polymer as a monomer 1 constituting the conductive polymer.
A conductive resin composition comprising a conductive resin composition dispersed and contained in a ratio such that the number of sulfonic acid groups per molecule is 0.06 to 0.6, and treating the composition with a solution of lithium hydroxide or lithium alkoxide. This is an alkali treatment method for a resin composition.
【０００６】本発明の第２は、導電性ポリマー中に、ス
ルホン酸基を１個又は２個有するアルキルスルホン酸
を、前記導電性ポリマーを構成するモノマー１分子当た
りのスルホン酸基の数が０．０６〜０．６となるような
割合で分散含有した導電性樹脂組成物中のスルホン酸基
の水素イオンの５０％以上がリチウムイオンで置換され
てなることを特徴とするアルカリ処理導電性樹脂組成物
である。A second aspect of the present invention is that an alkyl sulfonic acid having one or two sulfonic acid groups is contained in the conductive polymer so that the number of sulfonic acid groups per monomer molecule constituting the conductive polymer is zero. An alkali-treated conductive resin, wherein 50% or more of hydrogen ions of a sulfonic acid group in a conductive resin composition dispersed and contained at a ratio of 0.06 to 0.6 are substituted with lithium ions. A composition.
【０００７】本発明の好ましい実施態様として、前記導
電性ポリマーがポリアニリン、ポリピロール、ポリチオ
フェン又はポリフランである前記導電性樹脂組成物のア
ルカリ処理方法及びアルカリ処理導電性樹脂組成物があ
り、特に好ましい態様として前記導電性ポリマーがポリ
アニリンである前記導電性樹脂組成物のアルカリ処理方
法及びアルカリ処理導電性樹脂組成物がある。As a preferred embodiment of the present invention, there are an alkali treatment method and an alkali-treated conductive resin composition of the conductive resin composition in which the conductive polymer is polyaniline, polypyrrole, polythiophene or polyfuran, and particularly preferred embodiments. There is a method and an alkali-treated conductive resin composition of the conductive resin composition in which the conductive polymer is polyaniline.
【０００８】また、本発明の好ましい他の実施態様とし
て、前記スルホン酸基を１個又は２個有するアルキルス
ルホン酸がメタンスルホン酸、エタンスルホン酸、エタ
ンジスルホン酸又はブタンジスルホン酸である前記導電
性樹脂組成物のアルカリ処理方法及びアルカリ処理導電
性樹脂組成物があり、特に好ましい態様として前記アル
キルスルホン酸がエタンジスルホン酸である前記導電性
樹脂組成物のアルカリ処理方法及びアルカリ処理導電性
樹脂組成物がある。[0008] In another preferred embodiment of the present invention, the above-mentioned conductive alkyl sulfonic acid having one or two sulfonic acid groups is methanesulfonic acid, ethanesulfonic acid, ethanedisulfonic acid or butanedisulfonic acid. There are an alkali treatment method and an alkali-treated conductive resin composition of the resin composition, and as a particularly preferred embodiment, the alkali treatment method and the alkali-treated conductive resin composition of the conductive resin composition, wherein the alkylsulfonic acid is ethanedisulfonic acid. There is.
【０００９】前記導電性樹脂組成物中における導電性ポ
リマーとアルキルスルホン酸の割合は、前記導電性ポリ
マーを構成するモノマー１分子当たりのスルホン酸基の
数が０．０６〜０．６となるようにする。スルホン酸基
の数が０．０６未満では高性能が得られない。また、
０．６を超えると電極重量が増加し、性能が低下するの
で好ましくない。The ratio of the conductive polymer to the alkyl sulfonic acid in the conductive resin composition is such that the number of sulfonic acid groups per monomer molecule of the conductive polymer is 0.06 to 0.6. To If the number of sulfonic acid groups is less than 0.06, high performance cannot be obtained. Also,
If it exceeds 0.6, the weight of the electrode increases and the performance deteriorates, which is not preferable.
【００１０】本発明の方法の好ましい態様として、前記
水酸化リチウム又はリチウムアルコキシドの溶液が水酸
化リチウム又はリチウムアルコキシドのエタノール溶液
である導電性樹脂組成物のアルカリ処理方法がある。As a preferred embodiment of the method of the present invention, there is a method of treating a conductive resin composition in which the solution of lithium hydroxide or lithium alkoxide is an ethanol solution of lithium hydroxide or lithium alkoxide.
【００１１】アルカリ処理は、導電性樹脂組成物中のス
ルホン酸基の水素イオンの５０％以上がリチウムイオン
で置換されるまで行うのが好ましい。この置換割合が５
０％未満では効果が不十分となる。水素イオンをリチウ
ムイオンで置換することにより電池内部のガス発生を抑
制することができる。The alkali treatment is preferably performed until 50% or more of the hydrogen ions of the sulfonic acid groups in the conductive resin composition are replaced with lithium ions. This replacement ratio is 5
If it is less than 0%, the effect will be insufficient. By replacing hydrogen ions with lithium ions, gas generation inside the battery can be suppressed.
【００１２】[0012]
【発明の実施の形態】以下、ポリアニリンにエタンジス
ルホン酸を分散含有させた導電性樹脂組成物を例にとっ
て、本発明をさらに詳細に説明する。前記導電性樹脂組
成物は、例えばアニリン系化合物を原料モノマーとし、
エタンジスルホン酸と混合し、酸化重合させることによ
って得られる。ポリアニリンの重合度としては８量体以
上が好ましく、分子量範囲は１０００〜１００万程度で
ある。通常、原料モノマーであるアニリン系化合物４分
子に対して１分子程度のエタンジスルホン酸を使用すれ
ばアニリン系化合物１分子当たりのスルホン酸基の数が
０．０６〜０．６の範囲の導電性樹脂組成物を得ること
ができる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail by taking a conductive resin composition in which ethanedisulfonic acid is dispersed and contained in polyaniline as an example. The conductive resin composition, for example, using an aniline-based compound as a raw material monomer,
It is obtained by mixing with ethanedisulfonic acid and subjecting it to oxidative polymerization. The degree of polymerization of polyaniline is preferably octamer or more, and the molecular weight range is about 1,000 to 1,000,000. Usually, if about one molecule of ethanedisulfonic acid is used for four molecules of the aniline compound as the raw material monomer, the number of sulfonic acid groups per one molecule of the aniline compound is 0.06 to 0.6. A resin composition can be obtained.
【００１３】前記導電性樹脂組成物のアルカリ処理は、
該導電性樹脂組成物を水酸化リチウム又はリチウムアル
コキシドの溶液中に分散させ、攪拌することによって行
えばよい。リチウムアルコキシドとしてはリチウムエト
キシド、リチウムメトキシドなどが使用できるが、後述
するように溶媒としてはエタノールが一般的なので安定
性及び使いやすさの点でリチウムエトキシドが好まし
い。溶媒としてはポリアニリン中のエタンジスルホン酸
等のアルキルスルホン酸を溶解させず、水酸化リチウム
又はリチウムアルコキシドを分散又は溶解し、かつこれ
らのリチウム化合物に対して安定なものであれば特に制
限はないが、取扱の容易さ等からエタノールが好まし
い。[0013] The alkali treatment of the conductive resin composition comprises:
The conductive resin composition may be dispersed in a solution of lithium hydroxide or lithium alkoxide and stirred. As the lithium alkoxide, lithium ethoxide, lithium methoxide, or the like can be used. However, as described later, ethanol is generally used as the solvent, and lithium ethoxide is preferable in terms of stability and ease of use. The solvent is not particularly limited as long as it does not dissolve alkylsulfonic acid such as ethanedisulfonic acid in polyaniline, disperses or dissolves lithium hydroxide or lithium alkoxide, and is stable to these lithium compounds. Ethanol is preferred because of its ease of handling.
【００１４】水酸化リチウム又はリチウムアルコキシド
の使用量は、導電性樹脂組成物中のスルホン酸基１個当
たりのリチウム原子が０．８〜１．２個となるようにす
る。また、溶媒中の導電性樹脂組成物及びリチウム化合
物の濃度はそれぞれ１〜１０重量％及び１〜１０重量％
（リチウムアルコキシドの場合は１〜５重量％）の範囲
とするのが好ましい。１重量％未満では大量の処理液が
必要となり実用的でない。また、水酸化リチウムの場合
は１０重量％、リチウムアルコキシドの場合は５重量％
を超えるとポリマーがゲル化する場合がある。なお、ア
ルカリ処理の条件としては常温付近で２時間程度攪拌す
るのが一般的である。The amount of lithium hydroxide or lithium alkoxide used is such that the number of lithium atoms per sulfonic acid group in the conductive resin composition is 0.8 to 1.2. The concentrations of the conductive resin composition and the lithium compound in the solvent are 1 to 10% by weight and 1 to 10% by weight, respectively.
(1 to 5% by weight in the case of lithium alkoxide). If it is less than 1% by weight, a large amount of processing liquid is required, which is not practical. In the case of lithium hydroxide, 10% by weight, and in the case of lithium alkoxide, 5% by weight.
If it exceeds, the polymer may gel. In addition, as a condition of the alkali treatment, it is general that stirring is performed at about normal temperature for about 2 hours.
【００１５】このアルカリ処理により導電性樹脂組成物
に含まれるアルキルスルホン酸のスルホン酸基の水素イ
オンの５０％以上がリチウムで置換される。この処理に
より導電性樹脂組成物はＮ−メチルピロリドン（ＮＭ
Ｐ）やＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）など
の溶媒に部分的に可溶となり、電極への成形が容易とな
る。また、アンモニア水による処理の場合に比較して、
サイクル劣化も少なく、長寿命化する効果がある。さら
に、この処理によりリチウムイオンが導入された導電性
樹脂組成物は、リチウム電池に適用した際にリチウムイ
オンのインターカレーションが容易になるという利点も
ある。By this alkali treatment, 50% or more of the hydrogen ions of the sulfonic acid group of the alkylsulfonic acid contained in the conductive resin composition are replaced with lithium. By this treatment, the conductive resin composition becomes N-methylpyrrolidone (NM
It becomes partially soluble in solvents such as P) and N, N-dimethylacetamide (DMAc), which facilitates molding into electrodes. Also, compared to the case of treatment with ammonia water,
There is little cycle deterioration and there is an effect of extending the life. Further, the conductive resin composition into which lithium ions have been introduced by this treatment has an advantage that lithium ions can be easily intercalated when applied to a lithium battery.
【００１６】[0016]
【実施例】以下、実施例により本発明をさらに具体的に
説明する。 （実施例１〜６）本発明の方法により導電性樹脂組成物
のアルカリ処理を行い、得られた処理生成物を用いて電
極を形成し充放電試験を行った。先ず、エタンジスルホ
ン酸０．１モルの水溶液とアニリン０．１モルとを混合
し、過硫酸アンモニウム０．１モルを添加したのち、−
２〜０℃で５時間攪拌して反応させて導電性樹脂組成物
を得た。得られた組成物はアニリン１分子に対しエタン
ジスルホン酸０．２分子（アニリン１分子に対するスル
ホン酸基：０．４個）を含有していた。The present invention will be described more specifically with reference to the following examples. (Examples 1 to 6) The conductive resin composition was subjected to an alkali treatment according to the method of the present invention, and an electrode was formed using the treatment product obtained, and a charge / discharge test was performed. First, an aqueous solution of 0.1 mol of ethanedisulfonic acid and 0.1 mol of aniline are mixed, and 0.1 mol of ammonium persulfate is added.
The mixture was reacted by stirring at 2 to 0 ° C. for 5 hours to obtain a conductive resin composition. The obtained composition contained 0.2 molecules of ethanedisulfonic acid per aniline molecule (0.4 sulfonic acid groups per aniline molecule).
【００１７】リチウムに換算して１４．５ミリモルを含
む水酸化リチウム（ＬｉＯＨ）又はリチウムエトキシド
（ＥｔＯＬｉ）のエタノール溶液を所定濃度に調製し、
アルカリ処理溶液とした。このアルカリ処理溶液に、前
記により調製した導電性樹脂組成物１ｇを添加、混合
し、２５℃で２時間攪拌してアルカリ処理した。処理
後、ろ別して減圧乾燥しアルカリ処理導電性樹脂組成物
を得た。得られたアルカリ処理導電性樹脂組成物中のス
ルホン酸基の水素イオンのほぼ全量がリチウムイオンで
置換されていた。An ethanol solution of lithium hydroxide (LiOH) or lithium ethoxide (EtOLi) containing 14.5 mmol in terms of lithium is adjusted to a predetermined concentration,
An alkali treatment solution was used. To the alkali-treated solution, 1 g of the conductive resin composition prepared as described above was added, mixed, and stirred at 25 ° C. for 2 hours to carry out alkali treatment. After the treatment, the mixture was filtered and dried under reduced pressure to obtain an alkali-treated conductive resin composition. Almost all of the hydrogen ions of the sulfonic acid groups in the obtained alkali-treated conductive resin composition were replaced with lithium ions.
【００１８】水酸化リチウム溶液の濃度がそれぞれ１、
５、１０重量％のものを実施例１〜３とし、リチウムエ
トキシドの濃度がそれぞれ１、３、５重量％のものを実
施例４〜６とした。得られたアルカリ処理導電性樹脂組
成物の収率を表１及び表２に示す。収率はアニリン４分
子にエタンジスルホン酸が１分子存在すると仮定して、
そのエタンジスルホン酸にリチウムイオンが１００％付
加したときの重量を理論収量とし、（収量／理論収量）
×１００％として算出した。Each of the lithium hydroxide solutions has a concentration of 1,
Those having 5, 10% by weight were Examples 1-3, and those having lithium ethoxide concentrations of 1, 3, 5% by weight were Examples 4-6. Tables 1 and 2 show the yields of the obtained alkali-treated conductive resin compositions. The yield is based on the assumption that one molecule of ethanedisulfonic acid is present in four molecules of aniline,
The weight when 100% of lithium ions are added to the ethanedisulfonic acid is defined as the theoretical yield, and (yield / theoretical yield)
× 100% was calculated.
【００１９】それぞれ水酸化リチウム１重量％及び５重
量％の溶液で処理した実施例１及び２と、リチウムエト
キシド１重量％及び３重量％の溶液で処理した実施例４
及び５の試料をＮＭＰと混合してスラリ化し、型に流し
込み、乾燥させて直径３ｃｍ、厚さ２００μｍの電極を
作製した。この電極を正極とし、負極にＬｉ、電解液と
してＬｉＣｌＯ4 を１モル／リットル含むプロピレンカ
ーボネート（ＰＣ）を使用して二次電池を作製し、充放
電試験を行った。充電は０．１ｍＡ／ｃｍ2 で４．０Ｖ
まで充電し、３０分休止後放電した。放電は０．１ｍＡ
／ｃｍ2 で２．８Ｖまで放電し、３０分休止後に充電す
るサイクルを繰り返した。Examples 1 and 2 treated with 1% and 5% by weight solutions of lithium hydroxide and Example 4 treated with 1% and 3% by weight solutions of lithium ethoxide, respectively.
And 5 were mixed with NMP to form a slurry, cast into a mold, and dried to produce an electrode having a diameter of 3 cm and a thickness of 200 μm. A secondary battery was prepared using this electrode as a positive electrode, Li as a negative electrode, and propylene carbonate (PC) containing 1 mol / L of LiClO 4 as an electrolytic solution, and performed a charge / discharge test. Charging is 4.0 V at 0.1 mA / cm 2
The battery was discharged after a 30-minute pause. Discharge is 0.1mA
The cycle of discharging at 2.8 V / cm 2 to 2.8 V and charging after resting for 30 minutes was repeated.
【００２０】このときのサイクル劣化率を表１及び表２
に示し、さらに実施例１の試料について活物質当たりの
エネルギー密度〔Ｗｈ／ｋｇ〕を算出し、この値とサイ
クル数との関係を図１に示した。なお、ここでいうサイ
クル劣化率は、最高エネルギー密度以降の各サイクル毎
のエネルギー密度低下率の平均値である。また、エネル
ギー密度は（電流値〔Ａ〕×平均放電電圧〔Ｖ〕×時間
〔ｈ〕÷正極粉体重量〔ｋｇ〕）で表される。The cycle deterioration rates at this time are shown in Tables 1 and 2.
Further, the energy density [Wh / kg] per active material was calculated for the sample of Example 1, and the relationship between this value and the number of cycles is shown in FIG. Here, the cycle deterioration rate is an average value of the energy density reduction rates for each cycle after the highest energy density. The energy density is represented by (current value [A] × average discharge voltage [V] × time [h] / positive electrode powder weight [kg]).
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】（比較例）リチウム化合物のエタノール溶
液の代わりにアンモニア水５重量％を含むアセトン溶液
を使用した外は実施例１と同様にして実施例で使用した
のと同じ導電性樹脂組成物を処理し比較材を作製した。
この比較材を使用して実施例と同様にして二次電池を作
製し充放電試験を行い、活物質当たりのエネルギー密度
〔Ｗｈ／ｋｇ〕を算出し、この値とサイクル数との関係
を図１に示した。Comparative Example The same conductive resin composition as used in Example 1 was used in the same manner as in Example 1 except that an acetone solution containing 5% by weight of aqueous ammonia was used instead of the ethanol solution of the lithium compound. It processed and the comparative material was produced.
Using this comparative material, a secondary battery was prepared in the same manner as in the example, and a charge / discharge test was performed. The energy density per active material [Wh / kg] was calculated, and the relationship between this value and the number of cycles was shown. 1 is shown.
【００２４】実施例及び比較例の結果から、適性濃度の
リチウム化合物のエタノール溶液で処理した試料はいず
れも収率は８０％以上と高く、実用上問題はない。ま
た、従来技術であるアンモニア水−アセトン溶液で処理
したものに比較して著しくサイクル劣化率が小さいこと
がわかる。From the results of the Examples and Comparative Examples, all of the samples treated with an ethanol solution of a lithium compound having an appropriate concentration have a high yield of 80% or more, and there is no practical problem. In addition, it can be seen that the cycle deterioration rate is remarkably small as compared with the prior art treated with an ammonia water-acetone solution.
【００２５】[0025]
【発明の効果】本発明の方法によりアルカリ処理した導
電性樹脂組成物を電極活物質として用いた二次電池の性
能は、従来のアンモニア水で処理した導電性樹脂組成物
を使用したものに比較して充放電サイクルの繰り返しに
よる性能劣化割合が小さく、長寿命となる。すなわち、
本発明の方法は電極活物質として使用する導電性樹脂組
成物のアルカリ処理方法として効果的なものであり、こ
の方法によりアルカリ処理した導電性樹脂組成物は、高
性能の二次電池用電極活物質として極めて利用価値の高
いものである。The performance of a secondary battery using a conductive resin composition treated with alkali according to the method of the present invention as an electrode active material is compared with that of a conventional battery using a conductive resin composition treated with aqueous ammonia. As a result, the rate of performance degradation due to repeated charge / discharge cycles is small, and the life is extended. That is,
The method of the present invention is effective as an alkali treatment method for a conductive resin composition used as an electrode active material. It is extremely useful as a substance.
【図１】実施例１及び比較例におけるサイクル数と活物
質当たりのエネルギー密度との関係を示すグラフ。FIG. 1 is a graph showing the relationship between the number of cycles and the energy density per active material in Example 1 and Comparative Example.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｚ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI H01M 10/40 H01M 10/40 Z
Claims (7)
個又は２個有するアルキルスルホン酸を、前記導電性ポ
リマーを構成するモノマー１分子当たりのスルホン酸基
の数が０．０６〜０．６となるような割合で分散含有し
た導電性樹脂組成物を、水酸化リチウム又はリチウムア
ルコキシドの溶液で処理することを特徴とする導電性樹
脂組成物のアルカリ処理方法。1. A method according to claim 1, wherein a sulfonic acid group is contained in the conductive polymer.
A conductive resin composition containing an alkyl sulfonic acid having two or more alkyl sulfonic acids in a proportion such that the number of sulfonic acid groups per monomer molecule constituting the conductive polymer is 0.06 to 0.6. A method of treating a conductive resin composition with alkali, comprising treating with a solution of lithium hydroxide or lithium alkoxide.
ることを特徴とする請求項１に記載の導電性樹脂組成物
のアルカリ処理方法。2. The method according to claim 1, wherein the conductive polymer is polyaniline.
ホン酸であることを特徴とする請求項１又は２に記載の
導電性樹脂組成物のアルカリ処理方法。3. The method of claim 1, wherein the alkyl sulfonic acid is ethane disulfonic acid.
キシドの溶液が水酸化リチウム又はリチウムアルコキシ
ドのエタノール溶液であることを特徴とする請求項１〜
３のいずれか１項に記載の導電性樹脂組成物のアルカリ
処理方法。4. The method according to claim 1, wherein the solution of lithium hydroxide or lithium alkoxide is an ethanol solution of lithium hydroxide or lithium alkoxide.
4. The method for treating a conductive resin composition according to claim 3 with an alkali.
個又は２個有するアルキルスルホン酸を、前記導電性ポ
リマーを構成するモノマー１分子当たりのスルホン酸基
の数が０．０６〜０．６となるような割合で分散含有し
た導電性樹脂組成物中のスルホン酸基の水素イオンの５
０％以上がリチウムイオンで置換されてなることを特徴
とするアルカリ処理導電性樹脂組成物。5. The method according to claim 1, wherein the conductive polymer has one sulfonic acid group.
In a conductive resin composition containing an alkylsulfonic acid having two or more alkylsulfonic acids in a proportion such that the number of sulfonic acid groups per monomer molecule constituting the conductive polymer is 0.06 to 0.6. 5 of the hydrogen ion of the sulfonic acid group of
An alkali-treated conductive resin composition characterized in that 0% or more is replaced with lithium ions.
ることを特徴とする請求項５に記載のアルカリ処理導電
性樹脂組成物。6. The alkali-treated conductive resin composition according to claim 5, wherein the conductive polymer is polyaniline.
ホン酸であることを特徴とする請求項５又は６に記載の
アルカリ処理導電性樹脂組成物。7. The alkali-treated conductive resin composition according to claim 5, wherein the alkylsulfonic acid is ethanedisulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10071626A JPH11269390A (en) | 1998-03-20 | 1998-03-20 | Electroconductive resin composition and its alkali treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10071626A JPH11269390A (en) | 1998-03-20 | 1998-03-20 | Electroconductive resin composition and its alkali treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11269390A true JPH11269390A (en) | 1999-10-05 |
Family
ID=13466062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10071626A Withdrawn JPH11269390A (en) | 1998-03-20 | 1998-03-20 | Electroconductive resin composition and its alkali treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11269390A (en) |
-
1998
- 1998-03-20 JP JP10071626A patent/JPH11269390A/en not_active Withdrawn
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