JPH02240164A - Polyelectrolyte - Google Patents

Abstract

PURPOSE:To obtain a polyelectrolyte with excellent ionic conductivity around room temp. and stability by incorporating a specified polymer compd. contg. an alkylene oxide group and a dialkylsiloxane group and a salt of a metal ion of group Ia or IIa of the periodic table. CONSTITUTION:A polymer compd. contg. repeating units of the formula (wherein R is H or an alkyl; p is 1 or larger), namely contg. an alkylene oxide group and a dialkylsiloxane group and having a wt.-average MW (in terms of PS) of 2,000-5,000 and a salt of a metal ion of group Ia or IIa of the periodic table (e.g. LiCF3SO3) are incorporated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to polymer electrolysis, and particularly to polymer electrolysis that can withstand use in a wide temperature range and is chemically stable. [Prior art] In order to apply polymer electrolytes to static electricity prevention in plastics, batteries, and electrochemical devices, they must exhibit good ionic conductivity over a wide temperature range from low to high temperatures, and must have storage stability. It needs to be of good quality and the material should be easy to manufacture. However, no polymer electrolyte that comprehensively satisfies these required performances has been developed so far.

For example, conventionally, organic solvents such as 1,2-dimethoxyethane and brobylene carbonate have been widely used;
℃ is the limit for use in the high temperature range (damage to the T-pond, etc.).
Recently, as a method to improve the disadvantages of these organic solvents,
Research on the Polymer Electrolyte Prize is active, centering on polyethylene (non-oxide) (hereinafter abbreviated as PEO).

PEO is a salt of various metal ions belonging to group Ia or group Ila of the periodic table, such as LICFzSOi, Lid, L
iClO4, Nal, NaCF= SOs, KCF, S
o. etc., and exhibits relatively good ionic conductivity (for example, P. Vashist
a) Fast ion transport by et al.
In Solid (past IonTransport
in Solid), 1 3 1 pages (1979
), and has good storage stability. However, the ionic conductivity of PEO is highly temperature dependent, and although it shows good ionic conductivity above 60°C, the ionic conductivity deteriorates significantly below 20°C, making it difficult to use it in a wide temperature range. It was difficult to incorporate low molecular weight PE into versatile products.
As a method of improving ionic conductivity using O, a method of introducing low molecular weight PEO into the side chain of a vinyl polymer was proposed by D.G. Bannister (D, J.
Bannister et al.
er). 2 5, 1600K (1984), and D.F. Schreiber (1984) describes a method of introducing low molecular weight PEO into the side chain of polyphosphazene.
Journal of the American Chemical Society (JourIIal or
American Chemical Society
) 106@, page 6852 (1984). However, although this polymeric rice grain forms a complex with Li salt, its ionic conductivity at temperatures below 20'C was insufficient. Furthermore, a material in which low-molecular IEtPEo is introduced into a part of polysiloxane was published in the Journal of Power Sources (JourIIa) by Watanabe et al.
20, p. 327 (1987), the introduction rate of low-molecular-weight IPEO is low in this material, and therefore it cannot be applied unless a large amount of polymeric material is used. It was something. Furthermore, a polymer material that alternately combines low molecular weight PEO and silicon compounds was published by Nagaoka et al.
JourIIal of Polymer Science; JourIIal of Polymer Letter Edition
Science. , Polymer Letter
EdHion). It has been reported in Volume 22, Page 752 (1982) and Japanese Patent Application Laid-Open No. 60-216462, and
Same《BeG Hole (P) as a silicone material
．． G. Polmer Coa Communication (Polmer Coa Communication) by Hall et al.
2 Vol. 7, p. 98 (1986).
These polymer materials can be used at low temperatures from below 20°C to 60°C.
It provides high ionic conductivity over a wide temperature range up to temperatures above However, these polymer materials cannot avoid deterioration due to decomposition when they are stored or used in electronic devices for long periods of time.
This material was extremely disadvantageous in terms of practical application. [Problems to be Solved by the Invention] The first object of the present invention is to develop a novel product that is chemically stable without deterioration even during storage or long-term use, and has high ionic conductivity even at low temperatures below room temperature. The purpose of this invention is to provide a polymer electrolyte that is highly effective.

A second object of the present invention is to provide a new polymer electrolyte that has a low vapor pressure even at high temperatures. [Means for Solving the Problems] The above object is to provide at least a polymer compound containing a repeating unit represented by the following general formula (1) and the periodic table!
This was achieved by a polymer electrolyte containing a salt of a metal ion belonging to Group A or Group IIa. (In the formula, R represents a hydrogen atom or an alkyl group.

p is an integer greater than or equal to 1. ) The polymer material of the present invention has an alkylene oxide group in the main chain, so it has a high dielectric constant, has an excellent ability to dissolve and dissociate the supporting electrolyte, and also has a dialkylsiloxane group in the main chain. The glass transition point (Tg) is low《,
It is thought that it facilitates the movement of ions, and since it is a polymer compound, it has no boiling point and is thought to be highly stable at high temperatures. C* Hs Furthermore, by introducing -311 group, C*Hs
CHs Conventionally known - It is surprising that the polymer has Si-771, which has been unable to achieve with conventional polymer electrolysis, such as preventing deterioration at high temperatures, ensuring high ionic conductivity at low temperatures, and chemical This invention has fundamentally solved the issue of ensuring stability. Next, the present invention will be explained in detail. In general formula (1), R
is a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. p is an integer of 1 or more, preferably an integer of 2 to 20, particularly preferably 2 to 1
It is an integer of 2. The polymer compound of the present invention has the general formula (!
) may have multiple repeating units.

Examples of the remaining repeating units in the polymer compound of the present invention include dialkylbolysiloxanes (eg, dimethylbolysiloxane) and polyalkylene oxides, which can improve film-forming properties. The repeating unit represented by general formula (1) is 50 in the polymer.
It is preferable that the content is mol% or more. More preferably 80 mol% or more, particularly preferably 100 mol%
It is.

Representative examples of the repeating unit represented by the general formula (!) are shown below, but of course the repeating unit is not limited to these.

CzHs Ct Hs CtHs C Hs Ct Hs CtHs The weight average molecule IMW (in terms of boristyrene) of the polymer compound of the present invention is preferably 2000 to 5000.

As metal ions belonging to Group 1a or Group IIa of the periodic table, lithium, sodium, and potassium ions are preferable, and representative metal ion salts include L IcFs S
O3 , L tPFb , L i LLiClOa, L
iBF4, LiCFi Co! , L iSCN, NaC
F* SOs, Na I, Na Ci! Oa, Na
BF4, NaAs F&, KCFs So! ,K
SCN, KPFh. ．． Examples include Kcgo4 and KAsF*. More preferred is the above Li salt. These may be used alone or in combination of two or more, and NBua
It may be used in combination with other electrolytes such as BF4. The ratio of the polymer compound of the present invention to the metal ion salt is such that the polyalkylene oxide units are 2 to 50% of the metal ion salt.
It is preferable to contain the same amount. More preferably 《 is 6 to 30 times. If the ratio is too high, the Tg will increase and the ionic conductivity will decrease; if the ratio is too low, the effective ion concentration will decrease and the ionic conductivity will also decrease.

The polymer electrolyte of the present invention further includes a crosslinking agent, a polymer compound,
Other amphipathic compounds may also be added. As the crosslinking agent that may be added, those having a crosslinking group such as an epoxy group, an isocyanate group, an acid chloride group, an acid anhydride group, or an active ester group can be used. Examples of crosslinking agent compounds are shown below, but the invention is not limited to these. (1) Crosslinking agent compound example Compound example C-1 CH. coNti+cHz +-S-NCOC H s
C H x C C O N H + C I4 t +
TN C OC H z C O N H-+C H
t +-r-N C 0 Compound Example C-2 Compound Example C-3 NGO OCN-+CH. H. CH C O + C H t F"'r N CO] I Typical examples of the polymer compounds that may be added are shown below, but the invention is not limited to these. Those that are compatible with the molecular compound can be preferably used.

Compound Example C-4 →CHt -CH←τ OCOCHff Compound Example C-5 +CH11C Old Go Cj2 Compound Example C-6 -{CH yo CH20 Hi, Compound Example C-7 Thousand CH-CH! Ohi, CH, Compound Example C-8 CH. 10CH. -Chi1 COOCH. Further, as the amphipathic compound that can be added, any known amphipathic compound can be added.

Representative examples include those shown below, but are not limited to these.

Compound Example C-9 C+hHss-0÷cHz CH. OhiicH compound example C-10 C+tH*s-0{CHHz CH* OhoC+zHz
s Compound Example C-11 As a solvent for dissolving the polymer compound of the present invention and a salt of a metal ion, a solvent that can be used in a non-aqueous battery is generally used, and representative examples include acetonitrile, penzonitrile, etc. Nitrile: Carbonates such as brobylene carbonate and ethylene carbonate: Tetrahydrofuran, 3-methyl-tetrahydrofuran, 2-methyl-tetrahydrofuran, tetrahydrobyran, 1,3 dioxane, 1,4-dioxolane , l,2-dimethoxyethane and other ethers: T-butyrolactone, δ-butyrolactone and other lactoses: dimethyl sulfoxide, tetramethylene sulfone, dimethylformamide, etc., but are not necessarily limited to these. ．． These solvents may be used alone or in combination of two or more. The polymer electrolyte of the present invention can be used as a material for preventing static electricity in plastic materials, batteries, electrochromic displays, capacitors, and various other electrochemical devices.

A typical synthesis example of a polymer compound containing a repeating unit represented by general formula (1) of the present invention is shown below. Synthesis Example I Synthesis of a compound containing 100% of repeating units represented by Pl Tetraethylene glycol 10g (0.05g of)
and viridin 1. 9g (0.1 moffi) to 30mj of toluene! 7. Diethyl dichlorosilane was dissolved in a nitrogen gas flow at room temperature. 8g (0.0
A toluene solution of 5 mol) was added dropwise. then 50-6
The reaction was carried out at 0''C for 4 hours. After the reaction, the precipitated pyridine hydrochloride was removed, and the solvent and unreacted raw materials were distilled off under vacuum to obtain the desired product (colorless, slightly viscous oil). Yield 111. 5g (Yield 86%) Mwζ4500 The structure was confirmed by NMR and elemental analysis. [Example] The present invention will be explained in detail below using Examples, but is not limited to these. Example 1 A compound containing 100% of repeating units represented by Pi (Pi polymer) and LiCFsSO were added to acetonitrile at 40'C so that the composition ratio was as shown in Table 1.
It was dissolved in At this time, the concentration of P1 polymer was 10%. Thereafter, the solvent was removed under vacuum (lO-"~10-
'torr) at room temperature for 24 hours and at 60°C for 24 hours to completely remove the solvent and obtain a clear homogeneous viscous solution. (■■■) Furthermore, a compound containing 100% of repeating units represented by P2 instead of P1 polymer (referred to as P2 polymer)
, LiCj! instead of LiCF3 So, An identical solution was obtained except that 04 was substituted. (■■■
) Furthermore, an identical solution was obtained except that the PI polymer was replaced with a compound containing 100% of the repeating unit represented by P4 (referred to as P4 polymer). (
■■■) For comparison, the following compound (D-
Solution that is the same as Example 1 except that 1) was replaced.■■
○ was created. CH. For the viscous liquid thus obtained, a PT electrode of 1.8
Set at a distance of 0.1 Hz and immerse
Measure impedance at ~100,000 Hz (measurement temperature 25℃)
), Coj! Ionic conductivity was determined from the e-Coffie plot. In addition, the stability of the polymer was evaluated by the following method.

Each compound was dissolved in an acetonitrile-aqueous buffer solution with a pH of 4.2 at 25° C. (concentration: 5 wt%), and the decomposition into heptanomers was monitored using gel permeation chromatography (CPC).

The results of these measurements are shown in Table 1 and Figure 1. Table 1 As can be seen from Table 1, it is clear that Examples 1 to 1 of the present invention have good ionic conductivity near room temperature. Moreover, from FIG. 1, the polymer compound of the present invention is compared to the comparative example (D-
It is clear that the decomposition into monomers is suppressed and the stability is significantly improved compared to 1). [Effects of the Invention] According to the present invention, a polymer electrolyte having excellent ionic conductivity near room temperature and good stability can be obtained.

[Brief explanation of drawings]

FIG. 1 shows the decomposition properties of the PI polymer, P2 polymer, and compound D-1 in Example 1 into heptanomers. Patent Applicant Fuji Photo Film Co., Ltd. PI (hr) Procedural Amendment Heisei/2015, I & 1-2

Claims (1)

[Scope of Claims] A polymer compound containing at least a repeating unit represented by the following general formula (I) and a member of the periodic table Ia or IIa
A polymer electrolyte characterized by containing a salt of a metal ion belonging to the group A. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a hydrogen atom or an alkyl group. p is 1
is an integer greater than or equal to )