JPS63164176A - Organic secondary cell - Google Patents

Abstract

PURPOSE:To maintain the form with no fear of solution leakage, and to improve the electrical performance, by laminating the first conductive high polymer membrane electrode, a cross-linkage type high polymer film including electrolyte solution, and the second conductive high polymer membrane electrode, between the first and the second conductive foils for collection purpose, and composing an ion conductive medium fo a specific cross-linkage type high polymer and a specific electrolyte solution. CONSTITUTION:In an organic secondary cell with a cross-linkage type high polymer as an ion conductive medium, the first conductive high polymer membrane electrode 2, a cros-linkage type high polymer film 3 including electrolyte solution, and the second conductive high polymer membrane electrode 4 are laminated and formed between the first and the second conductive foils 1a and 1b. In this case, the ion conductive medium is composed of the cross-linkage type high polymer to absorb a lot of electrolyte solution, and the electrolyte solution absorbed to the cross-linkage type high polymer. Therefore, an organic secondary cell in which the form can be maintained with no fear of solution leakage, no separation is necessary, the production process is simple, and moreover, the electrical property such as output density and energy density are almost equal to that of the cell using only an electrolyte solution, can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an organic secondary battery using a crosslinked polymer as an ion conductive medium.

[Prior Art] As is well known, an electrolyte solution itself is generally used as an ion conductor in an organic secondary battery.

For example, Nippondenso Co., Ltd.'s published patent No. 59-49161 uses LIC104 dissolved in nolopyrene cargo as an ionic conductor. When using the electrolyte solution itself, battery characteristics such as power density and energy density are improved, but on the other hand, there is a risk of leakage, and when manufacturing an organic secondary battery, the construction work becomes complicated and the manufacturing cost increases. ,■Battery shape is limited,
When does the next disadvantage occur?

Furthermore, although there are few examples of using a solid electrolyte as an ion conductor, for example, Chiang (Natlo
nalBureau of 5standards 1
USA) paper (Polym@r.

Vol. 22.1454 (1981)), an I-lyethylene oxide group a I complex is used as the ionic conductor, and the operating temperature is 85°C. Also, what about Toshiba Corporation's published patent 58-75779? Some polymer resins such as ribinylidene fluoride contain electrolytes such as lithium perchlorate. When using a solid electrolyte, it is the opposite of using an electrolyte solution; generally, the output density, energy density, and battery characteristics are relatively inferior, but there is no fear of leakage, and the manufacturing process of organic secondary batteries is improved. It's easier and more versatile.

[Problems to be Solved by the Invention] However, conventional organic secondary batteries have the following drawbacks. That is, an electrolyte solution or a solid electrolyte is used as an ionic conductor in conventional organic secondary batteries. However, when an electrolyte solution is used, there are drawbacks such as a risk of leakage and a complicated manufacturing process of the organic secondary battery.

These drawbacks can be solved by using a solid electrolyte, but solid electrolytes have the disadvantages of low ionic conductivity and relatively poor battery characteristics such as output density and energy density.

The present invention was made in view of the above circumstances, and eliminates the risk of liquid leakage.
In addition to being able to maintain its shape without any separation, there is no need for a separator.
The fabrication process is simple, and the output density, energy density, and electrical properties can be improved using only an electrolyte solution.
The purpose is to provide an organic secondary battery that is almost equivalent to the #h combination.

[Means for Solving the Problems] The present invention provides an organic secondary battery using a crosslinked polymer as an ion conductive medium, in which a first conductive polymer film is provided between first and second conductive foils for current collection. An electrode, a crosslinked polymer film containing an electrolyte solution, and a second conductive polymer membrane electrode are laminated, and the ion conductive medium includes a crosslinked polymer capable of absorbing a large amount of an electrolyte solution, and a crosslinked polymer made of this crosslinked polymer. The gist is that the electrolyte solution is composed of an absorbed electrolyte solution.

[Function] It is possible to incorporate an appropriate amount of electrolyte solution to increase ionic conductivity, but the required characteristics of the crosslinked polymer, which is one of the constituent elements of the ion conductive medium, do not cause any fear of leakage. They are scales that hold their shape. Generally, when the crosslink density increases and the concentration of polar groups such as carboxyl groups and sulfone groups decreases, the amount of electrolyte solution taken up by the crosslinked polymer decreases.

Conversely, when the crosslinking density decreases and the polar group concentration increases, the amount of electrolyte solution taken up by the crosslinked polymer increases, making it difficult to maintain the shape in some cases. Therefore, a crosslinked polymer having appropriate crosslink density and polar group concentration is prepared by controlling the crosslink density and polar group concentration. This crosslinked polymer is impregnated with an electrolyte solution to prepare an ion-conducting medium that satisfies desired characteristics.

[Example] Hereinafter, one embodiment of the present invention will be described with reference to the drawings.

1 m and lb in the figure are a first conductive foil and a second conductive foil for current collection, respectively. A first conductive polymer membrane electrode (positive electrode) 2, an electrolyte solution-containing crosslinked polymer film 3, and a second conductive polymer membrane electrode (negative electrode) 4 are sequentially laminated between these conductive foils 1h and 1b. There are n.

A lead wire 5°5 is connected to each of the conductive foils 1* and lb, for example, at an applied voltage of 2 to 6 V and an ambient temperature of 20 to 3 V.
Charge at 0℃. On the other hand, the discharge is [iII, 100Ω~
Connect the IOMΩ load and wake it up.

It is possible to repeatedly charge and discharge in this way. Note that the properties (output density, energy density) depend on the degree of swelling of the crosslinked polymer containing the electrolyte solution, and as the degree of swelling increases, the properties tend to improve.

Next, the adjustment of each member of the organic secondary battery having the above structure will be explained.

That is, first, three-dimensional crosslinking is achieved by copolymerizing a monomer containing two or more vinyl groups and a vinyl type monomer in an appropriate ratio using a conventional method such as bulk polymerization, solution polymerization, or ionic polymerization. Prepare the polymer. When it is necessary to increase the content of electrolyte solution in a three-dimensionally crosslinked polymer, an appropriate polar group is introduced into the three-dimensionally crosslinked polymer. The battery characteristics (output density, energy density) of an organic secondary battery using the electrolyte solution-containing three-dimensional cross-linked polymer prepared in this way as an ion-conducting medium and a conductive polymer as an electrode were evaluated using only the electrolyte solution as an ion-conducting medium. When comparing the battery characteristics in the case of

Next, the adjustment of each member will be specifically explained.

ill 1! Preparation of crosslinked polymer containing solute solution a)
Stella 7'l (synthesis of styrene-divinylbenzene copolymer) First, the monomer styrene 15-30y-1, the crosslinking agent divinylbenzene 1-101F, the polymerization initiator (benzoyl peroxide or 2,2'-azo bisisobutyronitrile) from 0.1 to 0.41 are dissolved in each other.

Subsequently, this solution was cast into a glass plate shape, and then placed in a constant temperature bath set at 50 to 70°C under a nitrogen atmosphere for 10 to 20 hours.
A polymerized film is prepared by irradiation. If necessary, it is further post-cured at 100 to 120°C for 1 to 4 hours.

b) Stella f2 (sulfonation of styrene-divinylbenzene copolymer) First, the styrene-divinylbenzene co-M polymer film 1 prepared in step 1? and tetrachloroethane 10-3
0? 30~(5Q m
in to swell the film.

Subsequently, this was cooled to room temperature, after which 15 to 30 iP of chlorosulfonic acid was added little by little, and the mixture was incubated at room temperature for 3 to 6 hours.
r Stir. Then add glacial acetic acid until no more HC1 is generated and pour into a large amount of water. The film is then washed with acetone and water and dried.

If necessary, the sulfonic acid group concentration of the styrene-zovinylpenze copolymer film can be increased by heating with fuming sulfuric acid at 140 to 150°C for an appropriate period of time, and then washing and drying in the same manner. .

C) Stella 7'3 (sulfonated styrene-divinylbenzene copolymer film, containing electrolyte solution) First, in a polar solvent such as water, and then in a mixed solvent (organic solvent such as acetonitrile containing water). Electrolyte IWg is prepared by dissolving an electrolyte such as lithium perchlorate. Here, the electrolyte solution concentration is 0.02 to 0.2M, and the liquid temperature is 2
The temperature is 0 to 30°C. The sulfonated styrene-divinylbenzene copolymer film prepared in step 2 is immersed in this electrolyte solution to contain the electrolyte solution until a swelling equilibrium is reached. The degree of swelling is 1.5 to 3 and maintains a film-like shape.

(2) Preparation of polymer electrolyte/IJ pyrrole, ? Conductive polymers such as lithiophene and poly(3-methylthiophene) are prepared by electrolytic polymerization and applied to electrode materials for organic secondary batteries. As conditions for the electrolytic polymerization method, the monomers are pyrrole, thiophene, and 3-methylthiophene at 0.02 to 0.2M, and the supporting electrolyte is lithium perchlorate or tetraethylammonium perchlorate at 0.03 to 0.09M.

Propylene cargenate and acetonitrile are used as polar solvents, benzonitrile is used as a polar solvent, and an ITO-coated glass plate or platinum plate is used as an electrode for electrolysis, and the electrolysis voltage is 6 to 10v1.
Electrolytic polymerization is performed at a polymerization temperature of 20 to 30° C. and a polymerization time of 1 to 4 hours to form a polymer film, that is, polypyrrole, polythiophene, or poly(3-methylthiophene) on the positive electrode. The thus formed tL7 was immersed in a polar solvent such as propylene cargenate for 20 to 20 minutes.
A negative voltage of -6 to -1 OV was applied to the polymer film at 30°C for 1 to A h.
Dedoping is performed by applying r.

(3) Vapor deposition of metal foil for current collection First, the dedoped conductive polymer film prepared in (2) above is peeled off from an ITO-coated glass plate or platinum plate electrode for electrolysis. Subsequently, this product is vacuum dried at 40 to 80°C. Next, a metal foil such as gold or aluminum is deposited on one side of the conductive polymer film by vacuum deposition.

(4) Adjustment of ion-conducting medium film A cross-linked polymer film with appropriate cross-link density and polar group (sulfone group, etc.) concentration is dissolved in an electrolyte such as lithium perchlorate, and then impregnated with a polar solvent to adjust the degree of swelling. 2 to 3 times and prepare an ion conductive medium film as a solid-liquid composite.

According to the organic secondary battery according to the above embodiment, excessive compressive stress can be avoided by using a solid-liquid composite in which an electrolyte solution is incorporated into a crosslinked polymer having appropriate crosslinking density and lyophilicity as an ion conductive medium. As long as no pressure is applied, the shape can be maintained without fear of leakage.

Secondly, there is no need for a mono-quartet, and the manufacturing process of the organic secondary battery is simple, increasing its versatility. Moreover, the degree of swelling is 2
The characteristic values of the secondary battery using the polymer film 3 of No. 3 to 3 are almost the same as those of the following cases using only the electrolyte solution.

[Effects of the Invention] As described above, according to the present invention, the shape can be maintained without fear of liquid leakage, and the shape can be maintained without fear of liquid leakage. It is possible to provide an organic secondary battery that does not require a battery, has a simple manufacturing process, and has almost the same output density, energy density, and electrical characteristics as those using only an electrolyte solution.

[Brief explanation of the drawing]

The figure is an explanatory diagram of an organic secondary battery according to an embodiment of the present invention. 1 m, lb...conductive foil, 3...crosslinked polymer film containing electrolyte solution, 2,4...411 polymer membrane electrode,
5... Lead wire. Applicant Sub-Attorney Patent Attorney Takehiko Suzue Procedural Amendment 62FJ5/29/1929 Commissioner of the Patent Office Kuro 1) Akio Yu 1, Indication of Case Patent Application No. 1983-311549 2, Title of Invention Organic Secondary Battery 3 , Relationship with the case of the person making the amendment Patent applicant (820) Mitsubishi Heavy Industries, Ltd. 4, sub-agent UBE Building 3-7-2 Kasumigaseki, Chiyoda-ku, Tokyo 1
00 Is story 03 (502) 3181 (Main representative) ``Vyo+,)I''-・ 7. Contents of amendment (1) In the description box, page 1, line 15 and page 4, line 2 at the beginning, ``Crosslinked polymer " should be corrected to read "crosslinked polymer containing electrolyte solution." (2) “Ionic conductivity” on page 4, line 11 of the statement box, 1 below.
The sentence up to ``It is possible to maintain.'' in the 5th line is corrected as follows. (3) At the beginning of page 9, line 4 of the specification, it is possible to take in an appropriate amount of electrolyte solution, and it is possible to maintain the shape without causing any fear of leakage.'' (3) At the beginning of page 9, line 4 of the specification, .0
9MJ is corrected to rO, 01-0.09MJ. (4) In the 8th line of the same page of the specification, "6 to 10 V" is corrected to "4 to 10 V." (5) In line 14 of the same page of the specification, "-6 to -IO
Correct the text "VJ" to "-4~-10■". (6) In the third line of page 10 of the specification box, the word "adjustment" is corrected to "preparation."

Claims (1)

[Claims] In an organic secondary battery using a cross-linked polymer as an ion-conducting medium, a first conductive polymer film electrode, a cross-linked polymer film containing an electrolyte solution, and a second conductive polymer are placed between the first and second conductive foils for current collection. An organic secondary comprising layered molecular membrane electrodes, and wherein the ion conductive medium is composed of a crosslinked polymer capable of absorbing a large amount of electrolyte solution and an electrolyte solution absorbed by the crosslinked polymer. battery.