JPH0355707A - Manufacture of polymeric solid electrolyte - Google Patents

Abstract

PURPOSE:To improve ion conductivity by removing a solvent A from a mixed liquid including a predetermined amount of solvents A and B, as well as an ion dissociative salt by means of drying or soaking the solvent A in the solvent B that includes the ion dissociative salt. CONSTITUTION:From a mixed liquid that includes a solvent A that has compatibility with poly methyl meta-acrylate (PMA), a solvent B in which ion dissociative salt is soluble, and an ion dissociative salt, the solvent A is dried and removed or soaked in the solvent B that has ion dissociative salt, so as to manufacture a polymeric solid electrolyte. The solvent B is poorly soluble or non-soluble with PMA, and even when it is compatible with it, by including ion dissocative salt, it becomes non-soluble with PMA. The solid electrolyte includes the solvent B and the ion dissociative salt almost uniformly in PMA, and is essentially a solid, The ion dissociative salt is dissociated in the solvent B and since the ion moves in the solvent B, high ion conductivity is observed. For the solvent B, tetrahydrofuran, 4, 4-dimethyl-1, 3-dioxane, etc., are used.

Description

[Detailed Description of the Invention] Industrial Field of Application The present invention relates to solid polymer electrolytes used in chemical guppies such as primary batteries, secondary batteries, electromifuku displays, electrochemical sensors, iontophores, and capacitors. Conventional technology and its problems Conventional solid polymer electrolytes are composed of complexes of high molecular weight polyether and salt, complexes of polyether cross-linked products and salt, and main molecules with high molecular interlocking properties. The main materials were complexes of salts and polymers with polyether side chains in g+. These materials move ions through interlocking properties of polymers, and have a drawback of low ionic conductivity.

Purpose of the Invention The present invention has been made in view of the above-mentioned conventional problems.
The purpose of this invention is to provide a solid polymer electrolyte with high ionic conductivity.

Structure of the Invention In order to achieve the above-mentioned object, the present invention uses a solvent from a mixed solution containing a solvent A that is compatible with borimethyl p methacrylate, a solvent B that can dissolve an ion dissociable salt, and an ion dissociable salt. This is a method for producing a solid polymer electrolyte, which is characterized in that A is removed by drying or by immersion in a solvent B containing an ion-dissociative salt; This is a method for producing the polymer solid electrolyte which is bath-prone or insoluble. Also, the polymer solid electrolyte is made non-bath-proper with respect to polymethyl methacrylate because the solvent B contains an ion-dissociative salt. It is a manufacturing method.

The solid electrolyte is characterized by containing solvent B and ion dissociable salt more or less uniformly than K4 in polymethyl methacrylate, and being substantially solid.
Since the ions dissociate in the solvent and move in the solvent B, they exhibit high ionic conductivity.

Solvent B may be compatible with polymethyl methacrylate, swellable, or insoluble, but preferably insoluble or poorly soluble. This means that depending on the selection L of the solvent B, both the former case of a compatible type and the latter case of a microphase-separated type can be considered. However, in reality, the microphase-separated type is
One problem is appropriate and mechanical strength is maintained high.

Furthermore, in the present invention, depending on the combination of solvent B and salt,
Even if the insolubility increases and solvent B is compatible with 1-polymethyμ methacrylate, it may become insoluble and become phase-separated, which is one of the features of the present invention.

Solvent B capable of dissolving ionically dissociable materials includes tetrahydrofuran, 2-methytetrahydrofuran, 1.
3-dioxolane, 4,4-dimethyiv-1,3-dioxane, r-butyrolactone, ethylene carbonate,
Delobylene carbonate, butylene carbonate, sp
Hofun, 3-methips〃Hofun Start. -Petit μ ether, iso-petit μ ether, 1,2 dimethoxy V ethane, 1,2 ethoxymethoxy V ethane 1 meth A/#) glyme, methi ρ triglyme, methyl tetra glyme,
Examples include ethyl glyme and ethyl diglyme, but are not limited to these.

As an ion dissociative salt, LiOl! 04, LiB
F4, LiA8F6, LiOF3SO3, L
iPF6, LiI LiBrLiSON, N
aI, bi2131Q'A'IQ, LiOF5
002, NaBr, NaS(N, KSON,
MgOl2, M9(CJO4)2, (OH5)
4NBF4, (OHS)4NBr, (G2H5)4
NOIO4, (C2H5)4NI, (03H7)4N
Br, (n-04H9)4NBO4, (n-C4Hg
)4NI (n-05H11)4NI is preferred, but
Not limited.

EXAMPLE Hereinafter, the present invention will be explained with reference to an example. 14 parts of O polymethacrylate IE was dissolved in 86 parts by weight of methylene chloride, and 2.0 parts of lithium perchlorate was dissolved.
Parts by weight were dissolved. 20 parts by weight of propylene carbonate was added to this I# liquid to form a uniform mixed solution. After this mixed solution was uniformly cast on a Gafne plate, methylene chloride was removed by drying. The solid film after removal has a thickness of 20 μm, and its ionic conductivity is ~6X measured by the complex impedance method.
10-'S/c+++ (25°C).

Comparative Example 1 Boryethylene V-oxide having a molecular weight of 1 million was dissolved in methanol to form a 5 wt % solution. 0.4 parts by weight of lithium perchlorate was added to 100 parts by weight of this liquid to obtain a uniform l@H. The ionic conductivity measured by the solution gapedance method was IX10-78/cm (fi degree 25°C).

Comparative Example 2 150 parts by weight of methyl methacrylate of monomethoxylated polyethylene oxide having a molecular weight of 1000 was dissolved in 50 parts by weight of dimethoxyethane, and further 5 parts by weight of lithium perchlorate was added with a small amount of pezoyl peroxide. In addition, the solution in which the IC was uniformly dissolved was polymerized by heating.●This solution was cast onto a Teflon substrate.

Houniyorionden Jffl! 7X10-'S/Clll
(25°C).

Comparative Example 5 Pentafunctional polyethylene oxide Vdo 10 with molecule fi 3000
1 part by weight of lithium perchlorate was dissolved into a homogeneous solution. To this solution, 0884 parts by weight of hexamethylene diisocyanate and some tin acetate were added and mixed, and the resulting ionic conductivity was IX10-5S.
/am (25°C).

Effects of the Invention As described above, the present invention can provide a solid polymer electrolyte with high ionic conductivity, and therefore has extremely great industrial value.

Claims (3)

[Claims] (1) From a mixed solution containing solvent A that is compatible with polymethyl methacrylate, solvent B that can dissolve the ionically dissociative salt, and the ionically dissociable salt, solvent A is removed by drying or the ionically dissociative salt is contained. A method for producing a polymer solid electrolyte, which comprises removing the polymer solid electrolyte by immersing it in a solvent B. (2) The method for producing a solid polymer electrolyte according to claim 1, wherein the solvent B is poorly soluble or insoluble in polymethyl methacrylate. (3) The method for producing a solid polymer electrolyte according to claim 1, wherein the solvent B contains an ionically dissociable salt and thereby becomes insoluble in polymethyl methallylate.