JPS6097568A - Secondary battery - Google Patents

Secondary battery

Info

Publication number
JPS6097568A
JPS6097568A JP58205268A JP20526883A JPS6097568A JP S6097568 A JPS6097568 A JP S6097568A JP 58205268 A JP58205268 A JP 58205268A JP 20526883 A JP20526883 A JP 20526883A JP S6097568 A JPS6097568 A JP S6097568A
Authority
JP
Japan
Prior art keywords
vacuum
polyacetylene
electrode
secondary battery
treatment
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.)
Pending
Application number
JP58205268A
Other languages
Japanese (ja)
Inventor
Shigeoki Nishimura
西村　成興
Shinpei Matsuda
松田　臣平
Kazunori Fujita
一紀 藤田
Hiroyuki Sugimoto
博幸 杉本
Atsuko Toyama
遠山　厚子
Noboru Ebato
江波戸　昇
Hiroshi Hida
飛田　紘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Hitachi Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Denko KK, Hitachi Ltd filed Critical Showa Denko KK
Priority to JP58205268A priority Critical patent/JPS6097568A/en
Publication of JPS6097568A publication Critical patent/JPS6097568A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PURPOSE:To obtain a secondary battery having high coulomb efficiency and low self-discharge rate by applying heat-treatment in a vacuum to an electrode comprising a molecular compound having conjugated double bond in its principal chain. CONSTITUTION:Electrode using a high molecular compound having conjugated double bond in its principal chain is heated in a vacuum before use. For example, by heating in a vacuum (10<-1>mm.Hg or less), acetylene monomer, moisture or oxygen adsorbed on polyacetylene is removed to make clean the surface of the polyacetylene. Temperature of vacuum heat-treatment is preferable to set below the isomerization temperature (145 deg.C) of polyacetylene, and usually to set at 100 deg.C or less. The high degree of vacuum is preferable but the vacuum of 10<-2>- 10<-4>mm.Hg is actually used. By this treatment, a polymer secondary battery having low self-discharge rate and high coulomb efficiency is obtained.

Description

【発明の詳細な説明】 〔発明の利用分野〕 本発明は、電池に係り、特に充放電サイクルを繰り返す
２次電池に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a battery, and particularly to a secondary battery that undergoes repeated charging and discharging cycles.

〔発明の背景〕[Background of the invention]

主鎖に共役２束結合を有する高分子化合物を電極とする
２次電池が知られている［Ｊ、Ｃ，３，Ｃｈｅｍ。A secondary battery using a polymer compound having a conjugated two-bundle bond in its main chain as an electrode is known [J, C, 3, Chem.

Ｃ０ｍｍ、、　（１９８１）　３１７頁〜３１９頁〕。C0mm, (1981) pp. 317-319].

従来より知られているポリアセチレンを電極とした電池
の構造を第１図に示す。第１図において、符号１はポリ
アセチレン正極を、符号２はポリアセチレン負極を、符
号３は電解液を表わす。この電解液は不織布（材質ポリ
プロピレンなど）のセパレータに含浸させることもでき
る。この電極に電流を流すと電極として用いたポリアセ
チレンにドーパントイオンがドープされ、正極及び負極
となる。FIG. 1 shows the structure of a conventionally known battery using polyacetylene as an electrode. In FIG. 1, numeral 1 represents a polyacetylene positive electrode, numeral 2 represents a polyacetylene negative electrode, and numeral 3 represents an electrolytic solution. This electrolytic solution can also be impregnated into a separator made of nonwoven fabric (made of polypropylene, etc.). When current is passed through this electrode, the polyacetylene used as the electrode is doped with dopant ions, forming a positive electrode and a negative electrode.

負極側のポリアセチレンは、Ｌｌなどのアルカリ金属と
することも可能である。The polyacetylene on the negative electrode side can also be made of an alkali metal such as Ll.

今、厚さ２００μｍ１密度０．５ｇ／ｃｍ”のポリアセ
チレンを用い、ドーパントとして （Ｃ２Ｈｓ　）４　Ｎ　ＢＦ　４　、溶媒としてＣＨｓ
ＣＮを用い、電解液の濃度ｔ′ｉ１．０モル／ｌとした
。ポリアセチレンに対して電流密度５ｍＡ／ｃｍ２で４
モル−〇ドーピングを行ない、そのまま、開路状態に放
置した。放置時間とその時の自己放電率１１−一定放置
時間後のクーロン効率／放置時間零の時のクーロン効率
）ｘｉｏｏ）の関係を第２図に示した。１０時間後の自
己放電率は約２０チと大きい。Now, polyacetylene with a thickness of 200 μm and a density of 0.5 g/cm is used, (C2Hs)4NBF4 is used as a dopant, and CHs is used as a solvent.
CN was used, and the concentration t'i of the electrolytic solution was set to 1.0 mol/l. 4 at a current density of 5 mA/cm2 for polyacetylene.
Mol-〇 doping was performed and the circuit was left open. FIG. 2 shows the relationship between the standing time and the self-discharge rate at that time (11 - Coulombic efficiency after a certain standing time/Coulombic efficiency at zero standing time) (xioo). The self-discharge rate after 10 hours is as high as about 20 inches.

同様の電池を組み立て、充放電サイクルテストを、充放
電電流密度５ｍＡ／ｃｍ”、ドーピング率４モルチで１
０回行なった所、第３図の（２）に示す結果が得られた
。最大のクーロン効率でも９８％どまシであった。A similar battery was assembled and a charge/discharge cycle test was performed at a charge/discharge current density of 5 mA/cm'' and a doping rate of 4 molti.
When the test was repeated 0 times, the results shown in (2) in FIG. 3 were obtained. Even at the maximum Coulombic efficiency, it was only 98%.

〔発明の目的〕[Purpose of the invention]

本発明の目的は、クーロン効率が高く、自己数本発明を
概説すれば、本発明は２次電池の発明であって、主鎖に
共役２重粘合を有する高分子化合物を少なくとも一つの
電極に用いる２次電池において、高分子化合物を用いる
電極をあらかじめ真空加熱処理することを特徴とする。An object of the present invention is to provide a secondary battery with high coulombic efficiency and self-number of cells. A secondary battery used for this purpose is characterized in that the electrode using a polymer compound is subjected to a vacuum heat treatment in advance.

真空下（１０”＋ｍ＋Ｈｇ以下）において加熱処理する
ことによシボリアセチレンに吸着又は付着していた未反
応のアセチレン、水、酸素などが除去され、ポリアセチ
１７ンの表面を浄化することが可能である。この真空加
熱処理の条件としては、ポリアセチレンの異性化温度（
１４５Ｃ）以下が望ましく、実験の結果より１００Ｃ以
下で十分であることが判明した。真空度は高い方が望ま
しいが、実用的には、Ｉ　Ｑ　−”ｍＨｇ　〜１０−’
　ｔｔａｎＨｇで十分である。By heat treatment under vacuum (10"+m+Hg or less), unreacted acetylene, water, oxygen, etc. adsorbed or attached to the cibolyacetylene are removed, making it possible to purify the surface of the polyacetylene. The conditions for this vacuum heat treatment include the isomerization temperature of polyacetylene (
145C) or less is desirable, and experimental results have shown that 100C or less is sufficient. Although it is desirable that the degree of vacuum is high, in practice, I Q −”mHg ~10−’
ttanHg is sufficient.

本発明に用いる主鎖に共役２重粘合を有する高分子化合
物としては、（ＣＨ）！　、ポリフェニレン、ポリチェ
ニレン、ポリピロールなどが知られている。現在、２次
電池の電極として使用できる共役２重粘合を有する高分
子化合物は、ポリパラフェニレン、（ＣＨ）ｘが有望で
あるが、アセチレンの重合体である（ＣＨ）ｘが最良と
考えられる。（ＣＨ）ｘの重合方法は、洋種報告されて
いるし「合成金属」、１５頁、化学同人発行（１９８０
年）〕。本発明に用いる（ＣＨ）ｘは、いずれの重合方
法によシ製造されたものでも使用できる。As the polymer compound having a conjugated double viscosity in the main chain used in the present invention, (CH)! , polyphenylene, polythenylene, polypyrrole, etc. are known. Currently, polyparaphenylene, (CH)x, is a promising polymer compound with conjugated double viscosity that can be used as an electrode for secondary batteries, but (CH)x, a polymer of acetylene, is thought to be the best. It will be done. The polymerization method of (CH)
Year)〕. The (CH)x used in the present invention can be produced by any polymerization method.

このポリアセチレンに電気化学的にドーピングされうる
ドーパントイオンとしては、（ｉ）　ＰＦ６−１ＳｂＦ
６−１ＡｓＦｓ−，８ｂＣＬｅ−のどときＶｌｌ族の元
素ノハロゲン化アニオン、（ＩＩ）ＢＦ４−のごときＩ
ＩＩ　ａ族のハロゲンアニオン、（ｌｉｔ）　Ｉ　−（
Ｉ　ｓ−）　Ｂ　ｒ−１Ｃｔ−のごときハロゲンアニオ
ン、（ｉＶ）　Ｃｔｏ　４−のごとき過塩素酸アニオン
、（Ｖ）　Ｌ　ｉ“、Ｎａ２、Ｋ＋、Ｃ３“のどときア
ルカリ金属イオン、（ｖｉ）ＲａＮ責几：炭素数１〜２
０個の炭化水素基）のごとき４級アンモニウムイオン、
（Ｖｉｉｆ）　Ｒ４Ｐ　”　（几：炭素数１〜２０個の
炭化水素基）のごときホスホニウムイオンなどを挙げる
ことができる。上述の陰イオンドーパント及び陽イオン
ドーパントを与える化合物の具体例としては、Ｌ　ｉ　
ｐＦ　ａ、ＬｉＢＦ＜　、ＬｉＣ４０４、ＮａＩ、Ｎａ
Ｃｌ０ａ、ＫＣｌＯ４、（Ｃ２Ｈ５）４　ＮＢＦ　４　
、（Ｃ２Ｈ５）４　ＮＣ７０４、（Ｃ４Ｈ９）４ＮＢＦ
４　、（Ｃ４Ｈ９）４　ＮｅｔＯｎなどを挙げることが
できるが、必ずしもこれ等に限定されるものではなく、
これらのドーパントは単独又は混合して使用することが
できる。Dopant ions that can be electrochemically doped into this polyacetylene include (i) PF6-1SbF;
6-1AsFs-, 8bCLe-, Vll group element nohalogenated anion, (II) I such as BF4-
II a group halogen anion, (lit) I -(
I s-) halogen anions such as B r-1Ct-, (iV) perchlorate anions such as Cto 4-, (V) alkali metal ions such as Li", Na2, K+, C3", (vi) RaN Responsibility: Carbon number 1-2
0 hydrocarbon groups), quaternary ammonium ions,
Examples include phosphonium ions such as (Viif) R4P'' (几: a hydrocarbon group having 1 to 20 carbon atoms). Specific examples of compounds that provide the above-mentioned anion dopant and cation dopant include Li
pFa, LiBF< , LiC404, NaI, Na
Cl0a, KClO4, (C2H5)4 NBF4
, (C2H5)4 NC704, (C4H9)4NBF
4, (C4H9)4NetOn, etc., but are not necessarily limited to these.
These dopants can be used alone or in combination.

本発明において用いられる電解液は、上記ドーパントを
水又は非水溶媒に溶解したものであるが電池としては、
非水溶媒の方が望ましい。例えばニーデル類、ケトン類
、ニトリル類、アミン類、アミド類、硫黄化合物、塩素
化炭化水素類、エステル類、カーボネート類、ニトロ化
合物等を用いることができる。これらの代表例としては
、テトラヒトシフラン、２−メチルテトラヒドロンラン
、１．４ジオキサン、モノグリム、アセトニトリル、プ
ロピオニトリル、１，２−ジクロロエタン、ｒ−ブチロ
ラクトン、ジメトキシエタン、ギ酸メチル、フロピレン
カーボネート、ジメチルホルムアミド、ジメチルスルホ
キシド、ジメチルチオホルムアミド、スルホラン等を挙
げることができるが、これらは、単独又は混合して用い
ても良い。The electrolytic solution used in the present invention is one in which the above dopant is dissolved in water or a non-aqueous solvent, but as a battery,
Non-aqueous solvents are preferred. For example, needles, ketones, nitriles, amines, amides, sulfur compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds, etc. can be used. Typical examples of these include tetrahydrocifuran, 2-methyltetrahydronerane, 1.4 dioxane, monoglyme, acetonitrile, propionitrile, 1,2-dichloroethane, r-butyrolactone, dimethoxyethane, methyl formate, propylene carbonate, Dimethylformamide, dimethylsulfoxide, dimethylthioformamide, sulfolane, etc. can be mentioned, and these may be used alone or in combination.

本発明の電解質の濃度は、電解質（ドーノくント）及び
溶媒の種類によって異なるが、通常は０．００１〜１０
モル／ｌの範囲である。The concentration of the electrolyte of the present invention varies depending on the type of electrolyte and solvent, but is usually 0.001 to 10
The range is mol/l.

〔発明の実施例〕[Embodiments of the invention]

以−ト六本発明を実施例によシ更に具体的に説明するが
、本発明はこれらに限定されない。The present invention will now be described in more detail with reference to six examples, but the present invention is not limited thereto.

実施例１ ドーパントに（ＣｚＨ，５）４ＮＢＦ４、溶媒にＣＨ３
ＣＮ。Example 1 (CzH,5)4NBF4 as dopant, CH3 as solvent
C.N.

（ｌ［１，０モル／ｌで４モルチのドーピングを行なっ
た。用いたポリアセチレン膜の厚みは２００８ｍ１密度
は０．５ｇ／ｃｍ”である。このポリアセチレンを１０
　”　ｍｍＨｇの真空下６０Ｕで１時間処理を行なった
のち電池に組み立てた。電流密度５ｍＡ／ｃＩｎ”での
充放電サイクルテストの結果を第３図の■に示す。第１
サイクルよシフ５チのクーロン効率が得られ、最大のク
ーロン効率は９９％を示した。(Doping was carried out at 4 mol/l at 1.0 mol/l. The thickness of the polyacetylene film used was 2008 ml and the density was 0.5 g/cm.
After processing for 1 hour at 60 U under a vacuum of mmHg, it was assembled into a battery.The results of a charge/discharge cycle test at a current density of 5 mA/cIn are shown in Figure 3 (■). 1st
A Coulombic efficiency of 5 cycles and shifts was obtained, and the maximum Coulombic efficiency was 99%.

また、４モル−〇ドーピングを行ない、１０時間後の自
己放電率を測定したところ、７チであった。Further, when 4 mol-0 doping was carried out and the self-discharge rate was measured after 10 hours, it was found to be 7.

実施例２ ポリアセチレンを、１０−”　ｓｍＨｇの真空下、１０
０Ｃで１時間処理した。この膜を用い、実施例１と同様
の自己放電テストを行なったところ、１０時間後の自己
放電率は８チであった。Example 2 Polyacetylene was heated under a vacuum of 10-" smHg to
It was treated at 0C for 1 hour. Using this film, a self-discharge test similar to that in Example 1 was conducted, and the self-discharge rate after 10 hours was 8.

比較例 ポリアセチレンを１１０−２−Ｈの真空下、１２０Ｃで
１時間処理をした。この膜を用いて電池テストを行なっ
た所、初期のクーロン効率は５０チしか得られなかった
。また４モル−のドーピング率での１０時間後の自己放
電率は２５％と逆に未処理のポリアセチレンよシ増加し
た。Comparative Example Polyacetylene was treated under a vacuum of 110-2-H at 120C for 1 hour. When a battery test was conducted using this membrane, an initial Coulomb efficiency of only 50 inches was obtained. The self-discharge rate after 10 hours at a doping rate of 4 mol was 25%, which was an increase compared to untreated polyacetylene.

〔発明の効果〕〔Effect of the invention〕

主鎖に共役２型締合を有する高分子を電極に用いる２次
電池において、電極を真空下で加熱処理することによシ
吸着不純物の除去を行ない、自己放電率が低く、初期よ
りクーロン効率が高い高分子２次電池を提供できる。In secondary batteries that use polymers with conjugated 2-type compaction in the main chain as electrodes, adsorbed impurities are removed by heating the electrodes under vacuum, resulting in low self-discharge rates and Coulombic efficiency from the initial stage. It is possible to provide a polymer secondary battery with high

【図面の簡単な説明】[Brief explanation of the drawing]

第１図はポリアセチレンを電極とした電池の構造を示す
概略図、第２図は従来技術による電池の自己放電特性図
、第３図は従来技術及び本発明によシミ池の充放電サイ
クル特性図である。 １・・・ポリアセチレン正極、２・・・ポリアセチレン
負￥　１　口 コ 第　２０ ＆１蒔Ｍ（ｋ） 箔　３　口 ０　２　４　６　δ　１０ サイワ１し［］数　（ロ） 第１頁の続き ■発明者　杉　本　博　幸　日立市幸町３丁１所内 ■発明者　遠　山　厚　子　日立市幸町３丁１所内 ０発　明　者　江　波　戸　昇　日立市幸町３丁１所内 ０発　明　者　飛　１）　紘　日立市幸町３丁１所内Fig. 1 is a schematic diagram showing the structure of a battery using polyacetylene as an electrode, Fig. 2 is a self-discharge characteristic diagram of a battery according to the prior art, and Fig. 3 is a diagram of charging/discharging cycle characteristics of a stain battery according to the prior art and the present invention. It is. 1...Polyacetylene positive electrode, 2...Polyacetylene negative ¥1 Mouth 20 &1 Maki M(k) Foil 3 Mouth 0 2 4 6 δ 10 Size 1 [] Number (b) Continuation of page 1 ■Invention Person: Hiroyuki Sugimoto, 3-1 Saiwaimachi, Hitachi City ■Inventor: Atsuko Toyama, 3-1, Saiwaimachi, Hitachi City, 0 inventions Author: Noboru Ebato, 3-1 Saiwaimachi, Hitachi City, 0 inventions Author: Hi 1 ) Hiro 3-1 Saiwaimachi, Hitachi City

Claims (1)

【特許請求の範囲】 １、主鎖に共役２束結合を有する高分子を電極に用いる
電池において、電極をあらかじめ真空加熱処理すること
を特徴とする２次電池。 ２、特許請求の範囲第１項において、前記真空加熱処理
の加熱温度を１００Ｃ以下とすることを特徴とする２次
電池。[Scope of Claims] 1. A secondary battery using a polymer having a conjugated two-bundle bond in its main chain as an electrode, characterized in that the electrode is subjected to vacuum heat treatment in advance. 2. The secondary battery according to claim 1, wherein the heating temperature of the vacuum heating treatment is 100C or less.
JP58205268A 1983-10-31 1983-10-31 Secondary battery Pending JPS6097568A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58205268A JPS6097568A (en) 1983-10-31 1983-10-31 Secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58205268A JPS6097568A (en) 1983-10-31 1983-10-31 Secondary battery

Publications (1)

Publication Number Publication Date
JPS6097568A true JPS6097568A (en) 1985-05-31

Family

ID=16504164

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58205268A Pending JPS6097568A (en) 1983-10-31 1983-10-31 Secondary battery

Country Status (1)

Country Link
JP (1) JPS6097568A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6243065A (en) * 1985-08-19 1987-02-25 Showa Denko Kk non-aqueous secondary battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6243065A (en) * 1985-08-19 1987-02-25 Showa Denko Kk non-aqueous secondary battery

Similar Documents

Publication Publication Date Title
JP4158071B2 (en) Polymer electrolyte gel composition
US5176969A (en) Electrode for secondary battery
KR101041722B1 (en) Electrolyte including eutectic mixture and nitrile compound and electrochemical device having same
KR101055144B1 (en) Electrolyte including amide compound and electrochemical device having same
CN102160228B (en) Electrolyte containing eutectic mixture and electrochemical device containing same
JPH097896A (en) Electric double layer capacitor
JP7045616B2 (en) Positive electrodes and electrochemical devices for electrochemical devices, and methods for manufacturing them.
JP2004505432A (en) Polymer electrolyte
KR20160007366A (en) Binder for rechargeable lithium battery, separator for rechargeable lithium battery and rechargeable lithium battery
KR20090079166A (en) Electrolyte including eutectic mixture and electrochemical device having same
CN112928387A (en) Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm
JPH1131637A (en) Electric double layer capacitor, carbon material and electrode therefor
JP7382549B2 (en) electrochemical device
KR20180091585A (en) Cross-linked polymer for gel polymer electrolyte and manufacturing therof, gel polymer electrolyte and manufacturing therof, and electrochemical device including the same gel polymer electrolyte
JPS61206170A (en) Secondary battery and its electrode
JP2761212B2 (en) Energy storage device using non-aqueous electrolyte
JPH03171567A (en) Secondary battery
KR20100099963A (en) Electrolyte comprising borane compound and electrochemical device containing the same
JPS62176068A (en) Cylindrical polymer battery
KR101600024B1 (en) Electrolyte comprising amide compound and electrochemical device containing the same
JP2003297363A (en) Electrode material for electrochemical cell and electrochemical cell using the same
JPS6097562A (en) secondary battery
WO2022239746A1 (en) Binder for silicon negative electrode of lithium ion secondary battery
JPS60151978A (en) Battery
JPS61110975A (en) Organic electrolyte secondary battery