JPH0526305B2 - - Google Patents
Info
- Publication number
- JPH0526305B2 JPH0526305B2 JP58057574A JP5757483A JPH0526305B2 JP H0526305 B2 JPH0526305 B2 JP H0526305B2 JP 58057574 A JP58057574 A JP 58057574A JP 5757483 A JP5757483 A JP 5757483A JP H0526305 B2 JPH0526305 B2 JP H0526305B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- polynitrile
- acetylene
- discharging
- charging
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 20
- 238000007599 discharging Methods 0.000 claims description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 13
- 229920005554 polynitrile Polymers 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 description 8
- 229920001197 polyacetylene Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 polyphenylene Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- H01M4/36—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
Description
産業上の利用分野
本発明は、高分子物質を電極材料に用いた二次
電池に関するものである。
従来例の構成とその問題点
最近、高分子重合体にある種の物質をドープす
ると電気伝導性が向上し、ついには金属電導を示
すようなものが知られており、このような高分子
物質は合成金属と呼ばれている。その代表例とし
てポリアセチレンやポリフエニレンがある。
これらは、高分子主鎖の炭素原子のπ電子が共
役二重結合により主鎖の間で非局在化しており、
ある種の物質をドープすることにより高導電率を
示すようになる。
この種の高分子物質を電極材料に用いた新しい
タイプの二次電池が、例えば特開昭56−136469号
公報に記載されている。高分子物質を正極に用い
た場合の充放電反応は、高分子物質の電解液中の
陰イオンの取り込み（ドープ）による充電反応
と、陰イオンの放出（アンドープ）による放電反
応である。
高分子物質としてポリアセチレン（CH）o、電
解液として過塩素酸リチウムを例えばプロピレン
カーボネートに溶解した溶液を用いた場合の正極
の充放電反応を以下に示す。
（CH）o＋nx（ＣO4 -）
充電
−−→
−−←
放電〔CH（ＣO4）x〕o＋nxe (1)
このように高分子物質は、正極として機能する
ので、他の負極と組み合わせることにより、二次
電池を構成することができる。
この種の高分子物質としては、上記の他、ポリ
硫化フエニレン、ポリピロールあるいは水素原子
の若干がハロゲン原子、アルキル基、フエニル
基、アルキルフエニル基、ハロフエニル基などで
置換されたポリアセチレンなどが知られている。
一方、高分子物質を負極として用いる場合、こ
れと組み合わせる電解液としては、過塩素酸リチ
ウム（LiCO4）、硼フツ化リチウム（LiBF4）、
六フツ化リン酸リチウム（LiPE6）などのリチウ
ム塩を溶質とし、プロピレンカーボネートやテト
ラヒドロフランを溶媒とした有機電解液が知られ
ている。しかし、上記に示した高分子物質を電極
に用いた場合には、高率充放電が困難であるとい
う欠点があつた。
発明の目的
本発明の目的は、高率充放電が可能な正極用高
分子物質を提供することである。
発明の構成
本発明は、環化ポリニトリルアセチレンを正極
とし、電解液には、充放電により、環化ポリニト
リルアセチレン中に取り込まれたり、放出された
りする陰イオンからなる溶質を溶解したものを用
いることを特徴としている。
下記に環化ポリニトリルアセチレンの構造式を
示す。
(2)式に示すように環化ポリニトリルアセチレン
はＣ＝Ｎの二次結合、Ｃ＝Ｇの二重結合により共
役した電子系を有している。
環化ポリニトリルアセチレンは、(3)，(4)式に示
すように、ポリニトリルアセチレンを不活性雰囲
気中で加熱することにより環化反応が起つて生成
したり（(3)式）、ポリアクリロニトリルを酸化性
雰囲気で300℃に加熱することにより脱水素反応
と環化反応が起り生成する（(4)式）。
実施例の説明
実施例 １
電解液に１モル／の過塩素酸リチウムを溶解
させたプロピレンカーボネートを用いた。対極す
なわち負極として、大きさ２cm×２cm、厚さ１mm
のリチウム板を用い、また照合電極としてリチウ
ム板を用いた。正極材料には、比較例としてポリ
アセチレン及び(2)式に示した環化ポリニトリルア
セチレンを用いた。ポリアセチレンは大きさ２cm
×２cm、重量50mgのフイルムを用い、環化ポリニ
トリルアセチレは、粉末50mgを大きさ２cm×２cm
のシート状に圧縮成形したものを用いた。これら
の正極材料１を第１図に示すようにカーボン塗料
２を用いて集電体であるチタン板３に接着して電
極を構成した。
充放電試験は、すべて20℃で行つた。充電は正
極の電位が照合電極に対して＋4.2Vになるまで
行い、放電は＋2.0Vになるまで行つた。
第１サイクルの充放電は、0.12mAとし、第２
サイクル以降の充放電はすべて4mAで連続して
行つた。第２図には、第10サイクルにおけるそれ
ぞれの正極の充電曲線、放電曲線を示す。図中、
Ａはポリアセチレン、Ｂは環化ポリニトリルアセ
チレンである。また第１表には、第10サイクルに
おける充電容量、放電容量を示す。環化ポリニト
リルアセチレンが優れていることがわかる。
INDUSTRIAL APPLICATION FIELD The present invention relates to a secondary battery using a polymer substance as an electrode material. Structures of conventional examples and their problems Recently, it has been known that doping polymers with certain substances improves their electrical conductivity, and that they eventually exhibit metallic conductivity. are called synthetic metals. Representative examples include polyacetylene and polyphenylene. These are because the π electrons of carbon atoms in the polymer main chain are delocalized between the main chains due to conjugated double bonds.
By doping it with a certain type of substance, it exhibits high electrical conductivity. A new type of secondary battery using this type of polymer material as an electrode material is described in, for example, Japanese Patent Laid-Open No. 136469/1983. The charging and discharging reactions when a polymeric substance is used as a positive electrode include a charging reaction due to the incorporation of anions (doping) into the electrolytic solution of the polymeric substance, and a discharging reaction due to the release of anions (undoping). The charge/discharge reaction of the positive electrode is shown below when polyacetylene (CH) o is used as the polymeric material and a solution of lithium perchlorate dissolved in, for example, propylene carbonate is used as the electrolyte. (CH) o + nx (CO 4 - ) Charge −−→ −−← Discharge [ CH (CO 4 ) By doing so, a secondary battery can be constructed. In addition to the above, known polymeric substances of this type include polyphenylene sulfide, polypyrrole, and polyacetylene in which some of the hydrogen atoms are substituted with halogen atoms, alkyl groups, phenyl groups, alkylphenyl groups, halophenyl groups, etc. ing. On the other hand, when using a polymer material as a negative electrode, the electrolyte to be combined with it is lithium perchlorate (LiCO 4 ), lithium borofluoride (LiBF 4 ),
Organic electrolytes are known that use a lithium salt such as lithium hexafluorophosphate (LiPE 6 ) as a solute and propylene carbonate or tetrahydrofuran as a solvent. However, when the above-mentioned polymeric substances were used for electrodes, there was a drawback that high rate charging and discharging was difficult. OBJECT OF THE INVENTION An object of the present invention is to provide a polymeric material for a positive electrode that is capable of high rate charging and discharging. Structure of the Invention The present invention uses a cyclized polynitrile acetylene as a positive electrode, and an electrolytic solution containing a solute containing anions that are incorporated into or released from the cyclized polynitrile acetylene during charging and discharging. It is characterized by its use. The structural formula of cyclized polynitrile acetylene is shown below. As shown in formula (2), the cyclized polynitrile acetylene has an electron system conjugated with a C=N secondary bond and a C=G double bond. As shown in formulas (3) and (4), cyclized polynitrile acetylene is produced by a cyclization reaction (formula (3)) when polynitrile acetylene is heated in an inert atmosphere, or as shown in formulas (3) and (4). Oxidizes acrylonitrile When heated to 300°C in an atmosphere, dehydrogenation and cyclization reactions occur to form (Equation (4)). Description of Examples Example 1 Propylene carbonate in which 1 mol/mol of lithium perchlorate was dissolved in an electrolytic solution was used. As a counter electrode or negative electrode, size 2 cm x 2 cm, thickness 1 mm
A lithium plate was used as the reference electrode. As a comparative example, polyacetylene and cyclized polynitrile acetylene shown in formula (2) were used as positive electrode materials. Polyacetylene is 2cm in size
x 2cm, weight 50mg film, cyclized polynitrile acetylene powder 50mg, size 2cm x 2cm
The material was compression molded into a sheet shape. As shown in FIG. 1, these positive electrode materials 1 were adhered to a titanium plate 3 serving as a current collector using a carbon paint 2 to form an electrode. All charge/discharge tests were conducted at 20°C. Charging was performed until the potential of the positive electrode reached +4.2V with respect to the reference electrode, and discharging was performed until the potential of the positive electrode reached +2.0V. The first cycle charge/discharge is 0.12mA, and the second cycle is 0.12mA.
All charging and discharging after the cycle was performed continuously at 4 mA. FIG. 2 shows the charging curve and discharging curve of each positive electrode in the 10th cycle. In the diagram,
A is polyacetylene and B is cyclized polynitrile acetylene. Table 1 also shows the charging capacity and discharging capacity in the 10th cycle. It can be seen that cyclized polynitrile acetylene is superior.
【表】
実施例 ２
実施例１と同じ構成の正極を用い、電解液には
１モル／のヨウ化亜鉛（ZnI2）水溶液を用い
た。対極すなわち負極には亜鉛板を、照合電極に
は飽和甘汞電極を用いた。充放電は、全て正極が
飽和甘汞電極に対して＋0.16Vになるまで行い、
放電は−0.24Vになるまで行つた。第１サイクル
の充放電は0.12mAで行い、第２サイクル以降の
充放電はすべて4mAで行つた。
第２表には、第10サイクルにおける各正極の充
電容量、放電容量を示した。このように水溶液を
電解液とした場合にも、本発明の環化ポリニトリ
ルアセチレンが優れている。[Table] Example 2 A positive electrode having the same configuration as in Example 1 was used, and a 1 mol/zinc iodide (ZnI 2 ) aqueous solution was used as the electrolyte. A zinc plate was used as the counter electrode, that is, the negative electrode, and a saturated acetate electrode was used as the reference electrode. Charging and discharging were performed until the positive electrode reached +0.16V with respect to the saturated electrode.
The discharge continued until the voltage reached -0.24V. The first cycle of charging and discharging was performed at 0.12 mA, and the second and subsequent cycles were all performed at 4 mA. Table 2 shows the charge capacity and discharge capacity of each positive electrode in the 10th cycle. The cyclized polynitrile acetylene of the present invention is also excellent when an aqueous solution is used as the electrolyte in this way.
【表】
実施例１，２から環化ポリニトリルアセチレン
を正極とした場合充放電反応として、有機電解液
中あるいは水溶液中の過塩素酸イオンがヨウ素イ
オンなどの陰イオンの取り込みや放出を行わせる
ことができ、従来のポリアセチレンに比べ優れた
性能を示すことができる。
発明の効果
本発明によれば、高分子物質を正極に用いた二
次電池の充放電特性を向上させることができる。[Table] From Examples 1 and 2, when cyclized polynitrile acetylene is used as a positive electrode, perchlorate ions in the organic electrolyte or aqueous solution take in and release anions such as iodine ions as a charge/discharge reaction. It can exhibit superior performance compared to conventional polyacetylene. Effects of the Invention According to the present invention, it is possible to improve the charging and discharging characteristics of a secondary battery using a polymeric substance as a positive electrode.
第１図は実施例に用いた電極の縦断面図、第２
図は有機電解液中での各種正極の充放電曲線を示
す図である。
Figure 1 is a vertical cross-sectional view of the electrode used in the example, Figure 2
The figure is a diagram showing charge/discharge curves of various positive electrodes in an organic electrolyte.
Claims (1)
り込み、放出する高分子物質よりなる正極と、前
記の陰イオンを含む電解液を備え、前記高分子物
質が環化ポリニトリルアセチレンであることを特
徴とする二次電池。1 A negative electrode, a positive electrode made of a polymeric material that reversibly takes in and releases anions through charging and discharging, and an electrolytic solution containing the anions, wherein the polymeric material is cyclized polynitrile acetylene. Characteristic secondary batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58057574A JPS59184460A (en) | 1983-03-31 | 1983-03-31 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58057574A JPS59184460A (en) | 1983-03-31 | 1983-03-31 | Secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59184460A JPS59184460A (en) | 1984-10-19 |
| JPH0526305B2 true JPH0526305B2 (en) | 1993-04-15 |
Family
ID=13059617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58057574A Granted JPS59184460A (en) | 1983-03-31 | 1983-03-31 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59184460A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3506659A1 (en) * | 1985-02-26 | 1986-08-28 | Basf Ag, 6700 Ludwigshafen | COMPOSITE ELECTRODE |
| CA2223562A1 (en) | 1997-12-02 | 1999-06-02 | Hydro-Quebec | New electrode material derived from ionic polyquinoid compounds, and their uses, especially in electrochemical generators |
-
1983
- 1983-03-31 JP JP58057574A patent/JPS59184460A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59184460A (en) | 1984-10-19 |
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