JPS58112247A - Battery and storage battery using high molecular compound carrying iodine holding power as electrode - Google Patents
Battery and storage battery using high molecular compound carrying iodine holding power as electrodeInfo
- Publication number
- JPS58112247A JPS58112247A JP56212686A JP21268681A JPS58112247A JP S58112247 A JPS58112247 A JP S58112247A JP 56212686 A JP56212686 A JP 56212686A JP 21268681 A JP21268681 A JP 21268681A JP S58112247 A JPS58112247 A JP S58112247A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- battery
- iodine
- thienylene
- storage battery
- 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
Links
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
Abstract
Description
【発明の詳細な説明】
ヨウ素は陰イオンになり易い物質であり電池及び蓄電池
の正極活物質として適当なものの一つである。しかしそ
れにもかかわらずヨウ素を正極活物質として用いた電池
の作製例はあまり多くない。本発明はヨウ素が次式：
で表わされる基を繰返し単位とするポＩＪ（２１５−チ
ェニレン）（以下ポリマーＡと略称する）およびポリ（
３−メチル ２．５−チェニレン）（以下ポリマーＢと
略称する）と付加体を作り易く、しかもこの付加体があ
る程度の電気伝導性を有する性質を利用し”、ポリマー
ＡおよびポリマーＢとヨウ素の付加体を主成分とする物
質を正極合剤として用いて電池を作製すること及びこの
電池を二次電池（蓄電池）に応用することを内容とする
ものである。DETAILED DESCRIPTION OF THE INVENTION Iodine is a substance that easily becomes an anion and is one of the materials suitable as a positive electrode active material for batteries and storage batteries. However, despite this, there are not many examples of producing batteries using iodine as a positive electrode active material. The present invention uses poly(215-chenylene) (hereinafter abbreviated as polymer A) and poly(
It is easy to form an adduct with 3-methyl 2,5-thennylene) (hereinafter abbreviated as polymer B), and this adduct has a certain degree of electrical conductivity. The content of this study is to fabricate a battery using a substance whose main component is an adduct as a positive electrode mixture, and to apply this battery to a secondary battery (storage battery).
ポリマーＡ及びポリマーＢは主鎖に沿′つたπ−電子共
役系を有し、しかもイオウを含む基を繰シ返し単位とす
るために、ヨウ素と強い付加体を形成し１重合体の重量
と＃１ぼ同じ重畳のヨウ素を強く吸収する性質が萎る。Polymer A and Polymer B have a π-electron conjugated system along the main chain, and since they use sulfur-containing groups as repeating units, they form strong adducts with iodine, resulting in a decrease in the weight of one polymer. #1 The property of strongly absorbing the same superimposed iodine weakens.
しかも、この重合体とヨウ素の付加体はある程度の電気
伝導性を有する。Furthermore, the adduct of this polymer and iodine has a certain degree of electrical conductivity.
本発明は、この事実を電池および蓄電池の作製に利用し
たものでアシ、内部抵抗がそれほど大きくない電池、蓄
電池が得られる。また９本発明の蓄電池においては、充
電の際に金属ヨウ化物の電気分解によって陽極に生成す
るヨウ素はポリマーＡあるいはポリマーＢに強・く吸収
される。蓄電池の負極側電極体には、この金属ヨウ化物
の電気分解の際に陰極に生成する金属と同一の金属を用
いる次に本発明に述べる電池の一般的作製法について説
明する。The present invention takes advantage of this fact in the production of batteries and storage batteries, thereby producing batteries and storage batteries whose internal resistance is not so large. Furthermore, in the storage battery of the present invention, iodine produced at the anode by electrolysis of metal iodide during charging is strongly absorbed by polymer A or polymer B. The negative electrode body of the storage battery uses the same metal as the metal produced at the cathode during electrolysis of the metal iodide. Next, a general method for manufacturing the battery described in the present invention will be described.
まず所定量のポリマーＡあるいはポリマーＢ。First, a predetermined amount of polymer A or polymer B.
あるいはこれらの重合体を含有する物質にヨウ素を添加
する。この添加法としてはヨウ素蒸気を接触させる方法
、ヨウ素を含む溶液に浸す方法、ヨウ素の練シ込みによ
る方法等を用いる。このようにして得られたポリマーＡ
あるいはポリマーＢ。Alternatively, iodine is added to materials containing these polymers. As a method for this addition, a method of contacting with iodine vapor, a method of immersing in a solution containing iodine, a method of kneading iodine, etc. are used. Polymer A thus obtained
Or Polymer B.
あるいはこれらの重合体を含有する物質とヨウ素し、ま
たヨウ化亜鉛、 １ａｃ１等の溶液を電解質溶液として
用いて電池を作製する。Alternatively, a battery is produced by iodine with a substance containing these polymers and using a solution of zinc iodide, 1ac1, etc. as an electrolyte solution.
また、蓄電池はポリマーＡあるいはポリマーＢ、あるい
はこれらの重合体を含有する物質を炭素繊維製布、白金
板等の集電６体上に被覆した物質あるいはポリマーＡ、
ポリマーＢを成型した物質を正極に、金属ヨウ化物を電
解質として用い、相当うにすると、正極側で析出したヨ
ウ素はポリマーＡあるいはポリマーＢと付加体を形成す
る。この後に直流電圧を切り９両極を導線で結べば放電
が起とシミ力が得られる。In addition, storage batteries are made of polymer A, polymer B, or a substance containing these polymers coated on six current collectors such as carbon fiber cloth or platinum plates, or polymer A,
When a molded material of Polymer B is used as a positive electrode and a metal iodide is used as an electrolyte, the iodine deposited on the positive electrode side forms an adduct with Polymer A or B. After this, if the DC voltage is turned off and the 9 poles are connected with a conducting wire, a discharge will occur and a stain force will be obtained.
実施例１
分子量２．４００のポリマーＢを１６ｍｇとりクロロホ
ルム２−に溶解させたものをｌσＸ２ｆｆｉの長方形状
の白金板に塗布し、クロロホルムを自然蒸発法によシ除
く。次に、この膜状のポリマーＢを室温下でヨウ素蒸気
に２時間さらすと、６篇ｇのヨウ素がポリマーＢに吸収
された。このポリマーＢとヨウ素の付加体を用いて第１
図の電池を組みたてたところ、Ｌ３Ｖの起電力と１０ｍ
Ａの開放電流（初期値）が得られた。本実施例の場合、
第１図において集電体は白金板であシ、電解質溶液とし
ては０． Ｏｓ Ｗ１ｏｌ／１のｚｎ工２ の水溶液
を用いこれを１．５（７）×３５１の東洋濾紙株式会社
製ガラス濾紙（ＧＡ１００型）にしみ込ませた。また、
金属板としてはＩＩＭＸ２ｍの亜鉛板を用いた。Example 1 16 mg of Polymer B having a molecular weight of 2.400 was dissolved in chloroform 2- and applied to a rectangular platinum plate of lσ×2ffi, and the chloroform was removed by natural evaporation. Next, when this film-like polymer B was exposed to iodine vapor at room temperature for 2 hours, 6 g of iodine was absorbed into the polymer B. Using this adduct of polymer B and iodine, the first
When the battery shown in the figure was assembled, the electromotive force of L3V and 10m
The open circuit current (initial value) of A was obtained. In the case of this example,
In Fig. 1, the current collector is a platinum plate, and the electrolyte solution is 0. A 1.5 (7) x 351 glass filter paper (GA100 type) manufactured by Toyo Roshi Co., Ltd. was impregnated with an aqueous solution of OsW1ol/1 of ZnK2. Also,
A zinc plate of IIMX2m was used as the metal plate.
実施例２
クロロホルム不溶性粉末状ポリマーＡ３２６ｍ１Ｆを、
室温下、真空中で２日間ヨウ素蒸気にさらすと、１６１
Ｑのヨウ素を吸収する。得られたヨウ素付加体のうち１
００Ｑをとり、島津製作所製成型器（以下、成型器とい
う）を用いで室温下６０ｏｋｙ／ｃｄの圧力で固める。Example 2 Chloroform-insoluble powdered polymer A326m1F,
When exposed to iodine vapor for two days in a vacuum at room temperature, 161
Absorb Q's iodine. One of the obtained iodine adducts
00Q is taken and solidified at a pressure of 60oky/cd at room temperature using a molding machine manufactured by Shimadzu Corporation (hereinafter referred to as a molding machine).
このようにして作成した直径１．３ｃｒＩＨの円板状固
形物の一端に、導電性樹脂（フルウチ化学株式会社販売
のｍｌｅａｔｒｏａａｇ ＋５０２）を用いて鋼線を接
合する。A steel wire is bonded to one end of the disc-shaped solid body having a diameter of 1.3 cr IH thus created using a conductive resin (mleatroaag +502 sold by Furuuchi Chemical Co., Ltd.).
次に、この円板状固形物を陽極として用い、金属板を陰
極として用いて９図１と同様の電池を組立てる。ただし
９本集施例の場合９図１において集電体は用いず、電力
を得るための導線は直接。Next, a battery similar to that shown in FIG. 1 is assembled using this disk-shaped solid material as an anode and a metal plate as a cathode. However, in the case of the 9-piece collection embodiment, the current collector is not used in Figure 1, and the conductor for obtaining power is directly connected.
ポリマーＡとヨウ素からなる正極合剤に接続され溶液と
してＭｇ （ＮＯ３） ２ 水溶液（ｏ、 ｏ ｓ、
ｒｎｏ′ｖｌ）を用いこれを東洋濾紙株式会社副ガラス
ｊ戸紙（ＧＡ１００型）にしみこませて用いた時には、
起電力として１．３ｖが得られ、又、電流計により２ｍ
ｌの電流が流れることを確認した０電解質溶液をＮａＣ
１水溶液（０，３２ｍｏｖ’ｌ ）あるいはＫＣ１水溶
液（０３５ｍＯｖｌ）に変えても、はぼ同様の起電力と
電流値を得た。It is connected to a positive electrode mixture consisting of polymer A and iodine, and an aqueous Mg (NO3) 2 solution (o, o s,
rno'vl) and soaked it into Toyo Roshi Co., Ltd.'s sub-glass J door paper (GA100 type),
1.3v was obtained as an electromotive force, and 2m was obtained by the ammeter.
The electrolyte solution that was confirmed to have a current of
1 aqueous solution (0.32 mOv'l) or KC1 aqueous solution (0.35 mOvl), similar electromotive force and current values were obtained.
実施例３
分子量３０．０００のナイロツ−６を８７ｊ＋９とりギ
酸１−に溶かす。この溶液と２２■のクロロホルム不溶
性のポリマーＡをめのう製乳鉢中で混合しペースト状の
液を得る。この液を直径５ｃｒｎの導電性を有する円形
炭素繊維製布に均一に塗布し。Example 3 Nirotsu-6 with a molecular weight of 30.000 was taken in 87j+9 and dissolved in formic acid 1-. This solution and 22 cm of chloroform-insoluble polymer A were mixed in an agate mortar to obtain a paste-like solution. This solution was uniformly applied to a conductive circular carbon fiber cloth with a diameter of 5 crn.
ギ酸を自゛然蒸発法により除く。次にこのポリマームと
ナイロン−６の混合物の塗布面をヨウ素のベンゼン溶液
（０，ｙ ７ｆｌ／ １００ｍｏｌ）に１２時間接触さ
せると、３０譜のヨウ素が吸収された。このポリマーと
ヨウ素の付加体を用いて図１の装置を組立てたところ、
１．３Ｖの起電力と５０鮎の開放電流（初期値）が得ら
れた。また、この電池を直列に２個結合したものを用い
、５鮎の通電量によって発光する発光ダイオードを５０
分間連続して点灯することができた。本実施例の場合。Formic acid is removed by natural evaporation. Next, when the coated surface of the mixture of this polymer and nylon-6 was brought into contact with a benzene solution of iodine (0,y 7 fl/100 mol) for 12 hours, 30 units of iodine were absorbed. When the device shown in Figure 1 was assembled using this polymer and iodine adduct,
An electromotive force of 1.3V and an open current (initial value) of 50V were obtained. In addition, using two of these batteries connected in series, a light emitting diode that emits light with an amount of current of 50
I was able to turn on the light continuously for several minutes. In the case of this example.
第１図において集電体は炭素繊維製布であシ、電解質溶
液としては０．０８ ｍｏ１／ ｌのＺｎＩ２ 水溶液
を用いこれを直径５．５ｍの東洋濾紙株式会社製・ｒラ
スｊ戸紙（ＧＡＩＱＯ型）にしみ込ませた。また金属板
としては直径５ ｃｍ ｅ厚さ０．３ｍの亜鉛板を用い
、空気電池による影響を避けるために第１図の装置を窒
素ガス下に置いた。In Fig. 1, the current collector is made of carbon fiber cloth, and the electrolyte solution is a ZnI2 aqueous solution of 0.08 mol/l. GAIQO type). A zinc plate with a diameter of 5 cm and a thickness of 0.3 m was used as the metal plate, and the apparatus shown in Fig. 1 was placed under nitrogen gas to avoid the influence of the air battery.
実施例４
実施例２と同様の方法によシ、ポリマーＡ及びポリマー
Ｂを成型器を用いて成型し９種々の電解質溶液、金属板
を用いて実施例２の場合と同様な電池を組立て、下表に
示す□結果を得た。使用した重合体は約１００■であシ
、これに１０−５０１１Ｉ？のヨウ素を付加させた。電
解質の濃度は０．０３−ム 重合体 負極電極
電解質溶液 起電力（Ｖ）ｌ ポリ？
−ＡＭｇＫｅｒ水溶液 １．５２ ポ
リマーＡ Ｎｉ 、Ｎｉ工工水水溶液
０．６３ ポリマーＢ Ｏ（ｌ
Ｃ＋（ｌＩ２水溶液 ０８４ ポリ
マＢ Ｃｏ ０ＯＩ２
０．７５ ポリＷ Ｂ Ｚｎ
ＺｎＩ２プロピレンカーボネート溶液０９実施例５
分子量４４００のポリマーＢを６０Ｑとりクロロホルム
１０−に溶かす。この溶液を直径５ｃＩｎの導電性を有
する円板炭素繊維製布に均一に塗布し、クロロホルムを
自然蒸発法によシ除く。この物質を正極側に用い、第２
図の蓄電池を組み立てた。本実施例の場合、第２図にお
いて集電体は炭素繊維製布である。また金属ヨウ化物と
してはヨウ化亜鉛水溶液（０，１ｍｏ１／ ｌ）を用い
これを直径！＋、５ｔ’ｍの東洋濾紙株式会社製ガラス
濾紙（ＧＡＩ００型）にしみ込ませた。また金属板とし
ては直径５ｙｎ厚さ０．３ ｍｌｌ＋の□亜鉛板を用い
、空気電池による影響を避けるために第２図の装置を窒
素ガス下に置いた。北斗電工株式会社製ガルバノスタッ
トＨＡ−３０１型を用いて、ポリ−ｒ −Ｂ側（集電体
を含む）を陽極に金属板側を陰極にしてＩ Ｑ ＯｍＡ
の電流で２分間充電を行なうｏｔの後第２図において直
流電源をはずし、ポリマーＢ側（集電体を含む）と金属
板側を接続すると１．３ｖの起電力が得られた。Example 4 Polymer A and polymer B were molded using a molding machine in the same manner as in Example 2, and batteries similar to those in Example 2 were assembled using various electrolyte solutions and metal plates. The results shown in the table below were obtained. The polymer used was about 100cm, and 10-5011I? of iodine was added. Electrolyte concentration is 0.03-m Polymer Negative electrode
Electrolyte solution Electromotive force (V)l Poly?
-AMgKer aqueous solution 1.52 Polymer A Ni, Ni engineering water aqueous solution
0.63 Polymer B O(l
C+(lI2 aqueous solution 084 Polymer B Co 0OI2
0.75 Poly W B Zn
ZnI2 Propylene Carbonate Solution 09 Example 5 Polymer B having a molecular weight of 4400 is taken as 60Q and dissolved in chloroform 10-. This solution is uniformly applied to a conductive circular carbon fiber cloth having a diameter of 5 cIn, and the chloroform is removed by natural evaporation. This material is used on the positive electrode side, and the second
The storage battery shown in the figure was assembled. In the case of this embodiment, the current collector in FIG. 2 is made of carbon fiber cloth. Also, as the metal iodide, an aqueous solution of zinc iodide (0.1 mol/l) was used, and the diameter was measured. +, 5 t'm glass filter paper manufactured by Toyo Roshi Co., Ltd. (GAI00 type) was soaked. A □ zinc plate with a diameter of 5yn and a thickness of 0.3 ml+ was used as the metal plate, and the apparatus shown in Fig. 2 was placed under nitrogen gas to avoid the influence of the air battery. Using a galvanostat model HA-301 manufactured by Hokuto Denko Co., Ltd., I Q OmA was conducted with the poly-r-B side (including the current collector) as the anode and the metal plate side as the cathode
After charging for 2 minutes at a current of 200 volts, the DC power source was removed as shown in FIG. 2, and when the polymer B side (including the current collector) and the metal plate side were connected, an electromotive force of 1.3 V was obtained.
蓄電池）に応用する午とが可能であった０It was possible to apply it to storage batteries).
第１図は、電池の装置図。ｌは集電体、２はポリマーＡ
あ為いはポリマーＢとヨウ素の付加体よシ成る正極合剤
、３は繊維状物質にしみ込ませた電解質溶液、４は金属
板、５は電圧計又は電流計を示す。
第２図は、蓄電池（充電中）の装置図。ｌは集電体、２
はポリマーＡあるいはポリマーＢ、３は繊維状物質にし
み込ませた金属ヨウ化物、４は金属板、５は充電用直流
電源を示す。
特許出願人
山本隆−
第１図
第２図FIG. 1 is a diagram of the battery device. 1 is the current collector, 2 is the polymer A
1 is a positive electrode mixture consisting of an adduct of polymer B and iodine, 3 is an electrolyte solution impregnated into a fibrous material, 4 is a metal plate, and 5 is a voltmeter or an ammeter. FIG. 2 is a diagram of the storage battery (currently being charged). l is the current collector, 2
indicates polymer A or polymer B, 3 indicates metal iodide impregnated into a fibrous material, 4 indicates a metal plate, and 5 indicates a DC power source for charging. Patent applicant Takashi Yamamoto - Figure 1 Figure 2
Claims (1)
ニレン）およびポリ（３−メチル２．５−チェニレン）
とヨウ素の付加体を正極合剤の主成分として用いること
を特徴とする電池の作製０ を正極便電極体として用い、金属ヨウ化物を電解質とし
て用いることを特徴とする蓄電池の作製０[Claims] Poly(2゜5-chenylene) and poly(3-methyl-2,5-chenylene) having the group represented by as a repeating unit
Preparation of a battery characterized in that an adduct of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56212686A JPS58112247A (en) | 1981-12-25 | 1981-12-25 | Battery and storage battery using high molecular compound carrying iodine holding power as electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56212686A JPS58112247A (en) | 1981-12-25 | 1981-12-25 | Battery and storage battery using high molecular compound carrying iodine holding power as electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58112247A true JPS58112247A (en) | 1983-07-04 |
Family
ID=16626734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56212686A Pending JPS58112247A (en) | 1981-12-25 | 1981-12-25 | Battery and storage battery using high molecular compound carrying iodine holding power as electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58112247A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58220363A (en) * | 1982-06-01 | 1983-12-21 | トムソン‐セーエスエフ | Electrochemical device capable of using for storing energy |
| JPS6154156A (en) * | 1984-08-23 | 1986-03-18 | Ryuichi Yamamoto | New type cell |
| JP2013161653A (en) * | 2012-02-06 | 2013-08-19 | Toyota Industries Corp | Sulfur-based cathode active material and nonaqueous secondary battery |
-
1981
- 1981-12-25 JP JP56212686A patent/JPS58112247A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58220363A (en) * | 1982-06-01 | 1983-12-21 | トムソン‐セーエスエフ | Electrochemical device capable of using for storing energy |
| JPS6154156A (en) * | 1984-08-23 | 1986-03-18 | Ryuichi Yamamoto | New type cell |
| JP2013161653A (en) * | 2012-02-06 | 2013-08-19 | Toyota Industries Corp | Sulfur-based cathode active material and nonaqueous secondary battery |
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